Mid-Chain branched Alkoxylated Sulfate Surfactants

ABSTRACT

Mid-chain branched primary alkyl alkoxylated sulfate surfactants useful in laundry and cleaning compositions, especially granular and liquid detergent compositions. These surfactant mixtures are also suitable for formulation with other surfactants for the purpose of providing improved surfactant systems, especially for use in detergent compositions which will be used in laundry processes involving low water temperature wash conditions. The present invention also relates to novel mid-chain branched primary alkyl alkoxylated sulfate surfactants suitable for use in the surfactant mixtures.

CROSS REFERENCE

This is a continuation of PCT International Application Ser. No.PCT/US97/06471, filed Apr. 16, 1997; which claims priority toProvisional Application Ser. Nos. 60/015,521, filed Apr. 16, 1996;60/015,523, filed Apr. 16, 1996; and 60/032,035, filed Nov. 26, 1996.

FIELD OF THE INVENTION

The present invention relates to mid-chain branched primary alkylalkoxylated sulfate surfactants useful in laundry and cleaningcompositions, especially granular and liquid detergent compositions.These surfactant are also suitable for formulation with othersurfactants for the purpose of providing improved surfactant systems,especially for use in detergent compositions which will be used inlaundry processes involving low water temperature wash conditions. Thepresent invention also relates to novel mid-chain branched primary alkylalkoxylated sulfate surfactants suitable for use in the surfactantmixtures.

BACKGROUND OF THE INVENTION

Conventional detersive surfactants comprise molecules having awater-solubilizing substituent (hydrophilic group) and an oleophilicsubstituent (hydrophobic group). Such surfactants typically comprisehydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide,polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkarylhydrophobe usually containing from about 10 to about 20 carbon atoms.Accordingly, the manufacturer of such surfactants must have access to asource of hydrophobe groups to which the desired hydrophile can beattached by chemical means. The earliest source of hydrophobe groupscomprised the natural fats and oils, which were converted into soaps(i.e., carboxylate hydrophile) by saponification with base. Coconut oiland palm oil are still used to manufacture soap, as well as tomanufacture the alkyl sulfate ("AS") class of surfactants. Otherhydrophobes are available from petrochemicals, including alkylatedbenzene which is used to manufacture alkyl benzene sulfonate surfactants("LAS").

The literature asserts that certain branched hydrophobes can be used toadvantage in the manufacture of alkyl sulfate detersive surfactants;see, for example, U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25,1969. However, it has been determined that the beta-branched surfactantsdescribed in the '556 patent are inferior with respect to certainsolubility parameters, as evidenced by their Krafft temperatures. It hasfurther been determined that surfactants having branching towards thecenter of carbon chain of the hydrophobe have much lower Kraffttemperatures. See: "The Aqueous Phase Behavior of Surfactants", R. G.Laughlin, Academic Press, N.Y. (1994) p. 347.

Generally, alkyl sulfates are well known to those skilled in the art ofdetersive surfactants. Alkyl sulfates were developed as a functionalimprovement over traditional soap surfactants and have been found topossess improved solubility and surfactant characteristics. Linear alkylsulfates are the most commonly used of the alkyl sulfate surfactants andare the easiest to obtain. For example, long-chain linear alkylsulfates, such as tallow alkyl sulfate, have been used in laundrydetergents. However, these have significant cleaning performancelimitations, especially with the trend to lower wash temperatures.

Also, as noted hereinbefore, the 2-alkyl or "beta" branched alkylsulfate are known. In addition to U.S. Pat. No. 3,480,556 discussedabove, more recently EP 439,316, published Jul. 31, 1991, and EP684,300, published Nov. 29, 1995, describe these beta-branched alkylsulfates. Other recent scientific papers in the area of branched alkylsulfates include R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991),pp 1671-1676 which describes the surface tensions of a variety of"linear Guerbet" and "branched Guerbet"--class surfactants includingalkyl sulfates. "Linear Guerbet" types are essentially "Y-shaped", with2-position branching which is a long straight chain as in: ##STR1##wherein Z is, for example, OSO3Na. "Branched Guerbet" types are likewise2-position branched, but also have additional branching substitution, asin: ##STR2## wherein Z is, for example, OSO3Na. See also Varadaraj etal., J. Colloid and Interface Sci., Vol. 140, (1990), pp 31-34 relatingto foaming data for surfactants which include C12 and C13 alkyl sulfatescontaining 3 and 4 methyl branches, respectively (see especially p. 32).

Known alkyl sulfates also include:

1. Primary akyl sulfates derived from alcohols made by Oxo reaction onpropylene or n-butylene oligomers, for example as described in U.S. Pat.No. 5,245,072 assigned to Mobil Corp.

2. Primary alkyl sulfates derived from oleic-containing lipids, forexample the so-called "isostearyl" types; see EP 401,462 A, assigned toHenkel, published Dec. 12, 1990, which describes certain isostearylalcohols and ethoxylated isostearyl alcohols and their sulfation toproduce the corresponding alkyl sulfates such as sodium isostearylsulfate.

3. Primary alkyl sulfates, for example the so-called "tridecyl" typesderived from oligomerizing propylene with an acid catalyst followed byOxo reaction;

4. Primary alkyl sulfates derived from "Neodol" or "Dobanol" processalcohols: these are Oxo products of linear internal olefins or are Oxoproducts of linear alpha-olefins. The olefins are derived by ethyleneoligomerization to form alpha-olefins which are used directly or areisomerized to internal olefins and metathesized to give internal olefinsof differing chain-lengths;

5. Primary alkyl sulfates derived from the use of "Neodol" or "Dobanol"type catalysts on internal olefins derived from feedstocks which differfrom those normally used to make "Neodol" or "Dobanol" alcohols, theinternal olefins being derived from dehydrogenation of paraffins frompetroleum;

6. Primary alkyl sulfates derived from conventional (e.g.,high-pressure, cobalt-catalyzed) Oxo reaction on internal olefins, theinternal olefins being derived from dehydrogenation of paraffins frompetroleum;

7. Primary alkyl sulfates derived from conventional (e.g.,high-pressure, cobalt-catalyzed) Oxo reaction on alpha-olefins;

8. Primary alkyl sulfates derived from natural linear fatty alcoholssuch as those commercially available from Procter & Gamble Co.;

9. Primary alkyl sulfates derived from Ziegler alcohols such as thosecommercially available from Albermarle;

10. Primary alkyl sulfates derived from reaction of normal alcohols witha Guerbet catalyst (the function of this well-known catalyst is todehydrogenate two moles of normal alcohol to the corresponding aldehyde,condense them in an aldol condensation, and dehydrate the product whichis an alpha, beta-unsaturated aldehyde which is then hydrogenated to the2-alkyl branched primary alcohol, all in one reaction "pot");

11. Primary alkyl sulfates derived from dimerization of isobutylene toform 2,4,4'-trimethyl-1-pentene which on Oxo reaction to the aldehyde,aldol dimerization, dehydration and reduction gives alcohols;

12. Secondary alkyl sulfates derived from sulfuric acid addition toalpha- or internal-olefins;

13. Primary alkyl sulfates derived from oxidation of paraffins by stepsof (a) oxidizing the paraffin to form a fatty carboxylic acid; and (b)reducing the carboxylic acid to the corresponding primary alcohol;

14. Secondary alkyl sulfates derived from direct oxidation of paraffinsto form secondary alcohols;

15. Primary or secondary alkyl sulfates derived from various plasticizeralcohols, typically by Oxo reaction on an olefin, aldol condensation,dehydration and hydrogenation (examples of suitable Oxo catalysts arethe conventional Co, or more recently, Rh catalysts); and

16. Primary or Secondary alkyl sulfates other than of linear primarytype, for example phytol, farnesol, isolated from natural productsources.

Beyond such known alkyl sulfates, however, is a vast array of otherpossible alkyl sulfate compounds and mixtures whose physical propertiesmay or may not make them useful as laundry detergent surfactants.(I)-(XI) display just some of the possible variations (the salts aredepicted only as the common sodium salts). ##STR3##

These structures are also useful to illustrate terminology in thisfield: thus, (I) is a "linear" alkyl sulfate. (I) is also a "primary"alkyl sulfate, in contrast with (VII) which is a "secondary" alkylsulfate. (II) is also a "primary" alkyl sulfate--but it is "branched".The branching is exclusively in the "2-position" as in the so-called"linear Guerbet" alkyl sulfates: carbon-counting by convention startswith C1, which is the carbon atom covalently attached to the sulfatemoiety. (III) can be used to represent any one of a series of branchedalkyl sulfates which, when e is an integer having the value 1 orgreater, have only "non-2-position branching". According to conventionalwisdom, at least for linear surfactant compounds, the hydrocarbonportion needs to have at least 12 carbon atoms, preferably more, toacquire good detergency. The indices a,b,c,d,e,f,g,h,i,j,k,l,m,n,o,p,qcan, in principle, be adjusted to accommodate this need. Compound (VIII)is the alkyl sulfate derived from a naturally occurring branchedalcohol, phytol. Compound (IX) is a highly branched alkyl sulfate, whichcan, for example, be made by sulfating an alcohol derived fromdimerizing isobutylene and performing an Oxo reaction on the product.Compound (X), when q=14, is an isostearyl alkyl sulfate; anotherso-called "isostearyl" alkyl sulfate has the general structure(III)--such compounds can be made by sulfating an alcohol derived from amonomeric by-product of the dimerization of oleic acid having 18 carbonatoms, i.e., d+e=14 in (III). Compound (XI) is a "neo" alkyl sulfate.(XII) and (XIII) are substructures depicting "vicinal" (XII) and"geminal" or "gem" (XIII) dimethyl branching, respectively. Suchsubstructures can, in principle, occur in alkyl sulfates and othersurfactants. Conventional alkyl sulfates can, moreover, be eithersaturated or unsaturated. Sodium oleyl sulfate, for example, is anunsaturated alkyl sulfate. Unsaturated alkyl sulfates such as oleylsulfate can be relatively expensive and/or relatively incompatible withdetergent formulations, especially those containing bleach.

In addition to the above structural variations, complex, highly branchedprimary alkyl sulfate mixtures having quaternary carbon atoms in thehydrophobe are producible, for example by sulfation of Oxo alcohol madevia acid-catalyzed polygas reaction; moreover stereoisomerism, possiblein many branched alkyl sulfates, further multiplies the number ofspecies; and commercial alkyl sulfates can contain impurities includingthe corresponding alcohols, inorganic salts such as sodium sulfate,hydrocarbons, and cyclic byproducts of their synthesis.

One known material is sodium isostearyl sulfate which is a mixture ofmethyl and/or ethyl branches distributed along an otherwise linear alkylbackbone wherein the total number of carbons in the entire molecule areabout 18. This isostearyl "mixture" is prepared in low yield fromnatural source feedstocks (i.e. tall oil, soy, etc.) via a process whichresults in branching which occurs in an uncontrolled manner, and whichcan vary depending upon the source of the feedstock. EP 401,462,assigned to Henkel, published Dec. 12, 1990 describes certain isostearylalcohols and ethoxylated isostearyl alcohols and their sulfation toproduce the corresponding alkyl sulfates such as "sodium isostearylsulfate" (CAS 34481-82-8, sometimes referred to as "sodium isooctadecylsulfate").

Again, while R. G. Laughlin in "The Aqueous Phase Behavior ofSurfactants", Academic Press, N.Y. (1994) p. 347 describes theobservation that as branching moves away from the 2-alkyl positiontowards the center of the alkyl hydrophobe there is a lowering of Kraffttemperatures (for a 15% solution), such solubility observations teachnothing about the surfactancy of these compounds or their utility forincorporation into detergent compositions. In fact, both commercialpractice and the published literature are equivocal on the desirabilityof branching in the mid-chain region. This includes the above-notedpatent publications describing the beta-branched alkyl sulfates as thedesired branching, as well as Finger et al., "Detergent alcohols--theeffect of alcohol structure and molecular weight on surfactantproperties", J. Amer. Oil Chemists' Society, Vol. 44, p. 525 (1967) orTechnical Bulletin, Shell Chemical Co., SC: 364-80. These referencesassert, with respect to deleterious structural changes possible inalcohol sulfates that "moving a CH3 has a small effect". Data presentedin a table shows a decrease in cotton detergency of 29% and a decreasein foaming of 77% relative to unbranched primary alcohol sulfate at theC13 chainlength. Moreover JP 721232 describes a detergency negative forthe replacement of C11 linear primary alkyl sulfate with branchedprimary alkyl sulfate of unspecified branching.

In addition, K. R. Wormuth and S. Zushma, Langmuir, Vol. 7, (1991), pp2048-2053 describes technical studies on a number of branched alkylsulfates, especially the "branched Guerbet" type, derived from thehighly branched "Exxal" alcohols made by Exxon. Phase studies establisha lipophile ranking, that is a hydrophobe ranking, as follows: highlybranched≈double tail>methyl branched>linear. Assertedly, branchedsurfactants mix oil and water less effectively than linear surfactants.The efficiency ranking is linear>double tail>>methyl branched ≈highlybranched. From these results, it is not immediately evident whichdirection to take in the development of further improvements in branchedalkyl sulfates.

Thus, going beyond simple technical theories of how to achieve cleaningsuperiority of one pure surfactant compound versus another, thedeveloper and formulator of surfactants for laundry detergents mustconsider a wide variety of possibilities with limited (sometimesinconsistent) information, and then strive to provide overallimprovements in one or more of a whole array of criteria, includingperformance in the presence of complex mixtures of surfactants, trendsto low wash temperatures, formulation changes including builders,enzymes and bleaches, various changes in consumer habits and practices,and the need for biodegradability. In the context provided by thesepreliminary remarks, the development of improved surfactants for use inlaundry detergents and cleaning products is clearly a complex challenge.The present invention relates to improved alkyl alkoxylated sulfatesurfactants.

As will be seen from the disclosures hereinafter, it has nowunexpectedly been determined that certain alkyl alkoxylated sulfatecompositions containing mid-chain branching are preferred for use incleaning products, especially laundry compositions used under cool orcold water washing conditions (e.g., 20° C.-5° C.). Preferred are thecombination of two or more of these mid-chain branched primary alkylalkoxylated sulfate surfactants which provide a surfactant mixture thatis higher in surfactancy and has better low temperature watersolubility. These mixtures as produced comprise the mid-chain branchingdesirable for use in the surfactants of the present invention, or thesurfactant mixtures disclosed herein can be formulated by mixing thedesired amounts of individual mid-chain branched surfactants. Suchsuperior mixtures are not limited to combinations with other mid-chainbranched surfactants but (preferably) they can be suitably combined withone or more other traditional detergent surfactants (e.g., primary alkylsulfates; linear alkyl benzene sulfonates; linear alkyl ethoxylatedsulfates; nonionic surfactants; etc.) to provide improved surfactantsystems.

These mid-chain branched surfactants are obtainable in relatively highpurity making their commercialization cost effective for the formulator.Suitable product mixtures can be obtained from processes which utilizefossil-fuel sources. (The terms "derived from fossil fuels" or"fossil-fuel derived" herein are used to distinguish coal, natural gas,petroleum oil and other petrochemical derived, "synthetic" surfactantsfrom those derived from living natural resources such as livestock orplants such as coconut palms).

One such process is designed to provide branched reaction products whichare primarily (85%, or greater) alpha-olefins, and which are thenconverted into hydrophobes in an Oxo-reaction sequence. Such branchedalpha-olefins contain from about 11 to about 18 (avg.) total carbonatoms and comprise a linear chain having an average length in the 10-18region. The branching is predominantly mono-methyl, but some di-methyland some ethyl branching may occur. Advantageously, such process resultsin little (1%, or less) geminal branching, i.e., little, if any,"quaternary" carbon substitution. Moreover, little (less than about 20%)vicinal branching occurs. Of course, some (ca. 20%) of the overallfeedstock used in the subsequent Oxo-process may remain unbranched.Typically, and preferably from the standpoint of cleaning performanceand biodegradability, this process provides alpha-olefins with: anaverage number of branches (longest chain basis) in the 0.4-2.5 range;of the branched material, there are essentially no branches on carbons1, 2 or on the terminal (omega) carbon of the longest chain of thebranched material.

Following the formation and purification of the branched-chainalpha-olefin, the feedstock is subjected to an Oxo carbonylationprocess. In this Oxo-step, a catalyst (e.g., conventional cobaltcarbonyl) which does not move the double bond from its initial positionis used. This avoids the formation of vinylidene intermediates (whichultimately yield less favorable surfactants) and allows thecarbonylation to proceed at the #1 and #2 carbon atoms.

It is therefore an object of the present invention to provide mid-chainbranched primary alkyl alkoxylated sulfate surfactants with greater than14.5 carbon atoms useful in cleaning compositions. It is also an objectof the present invention to provide mixtures of the mid-chain branchedprimary alkyl alkoxylated sulfate surfactants which are formulatablewith other surfactants to provide cleaning compositions having one ormore advantages, including greater surfactancy at low use temperatures,increased resistance to water hardness, greater efficacy in surfactantsystems, improved removal of greasy or body soils from fabrics, improvedcompatibility with detergent enzymes, and the like.

BACKGROUND ART

U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25, 1969, EP 439,316,published by Lever Jul. 31, 1991, and EP 684,300, published by LeverNov. 29, 1995, describe beta-branched alkyl sulfates. EP 439,316describes certain laundry detergents containing a specific commercialC14/C15 branched primary alkyl sulfate, namely LIAL 145 sulfate. This isbelieved to have 61% branching in the 2-position; 30% of this involvesbranching with a hydrocarbon chain having four or more carbon atoms.U.S. Pat. No. 3,480,556 describes mixtures of from 10 to 90 parts of astraight chain primary alkyl sulfate and from 90 to 10 parts of a betabranched (2-position branched) primary alcohol sulfate of formula:##STR4## wherein the total number of carbon atoms ranges from 12 to 20and R1 is a straight chain alkyl radical containing 9 to 17 carbon atomsand R2 is a straight chain alkyl radical containing 1 to 9 carbon atoms(67% 2-methyl and 33% 2-ethyl branching is exemplified).

As noted hereinbefore, R. G. Laughlin in "The Aqueous Phase Behavior ofSurfactants", Academic Press, N.Y. (1994) p. 347 describes theobservation that as branching moves away from the 2-alkyl positiontowards the center of the alkyl hydrophobe there is a lowering of Kraffttemperatures. See also Finger et al., "Detergent alcohols--the effect ofalcohol structure and molecular weight on surfactant properties", J.Amer. Oil Chemists' Society, Vol. 44, p. 525 (1967) and TechnicalBulletin, Shell Chemical Co., SC: 364-80.

EP 342,917 A, Unilever, published Nov. 23, 1989 describes laundrydetergents containing a surfactant system in which the major anionicsurfactant is an alkyl sulfate having an assertedly "wide range" ofalkyl chain lengths (the experimental appears to involve mixing coconutand tallow chain length surfactants).

U.S. Pat. No. 4,102,823 and GB 1,399,966 describe other laundrycompositions containing conventional alkyl sulfates.

G.B. Patent 1,299,966, Matheson et al., published Jul. 2, 1975,discloses a detergent composition in which the surfactant system iscomprised of a mixture of sodium tallow alkyl sulfate and nonionicsurfactants.

Methyl- substituted sulfates include the known "isostearyl" sulfates;these are typically mixtures of isomeric sulfates having a total of 18carbon atoms. For example, EP 401,462 A, assigned to Henkel, publishedDec. 12, 1990, describes certain isostearyl alcohols and ethoxylatedisostearyl alcohols and their sulfation to produce the correspondingalkyl sulfates such as sodium isostearyl sulfate. See also K. R. Wormuthand S. Zushma, Langmuir, Vol. 7, (1991), pp 2048-2053 (technical studieson a number of branched alkyl sulfates, especially the "branchedGuerbet" type); R. Varadaraj et al., J. Phys. Chem., Vol. 95, (1991), pp1671-1676 (which describes the surface tensions of a variety of "linearGuerbet" and "branched Guerbet"--class surfactants including alkylsulfates); Varadaraj et al., J. Colloid and Interface Sci., Vol. 140,(1990), pp 31-34 (relating to foaming data for surfactants which includeC12 and C13 alkyl sulfates containing 3 and 4 methyl branches,respectively); and Varadaraj et al., Langmuir, Vol. 6 (1990), pp1376-1378 (which describes the micropolarity of aqueous micellarsolutions of surfactants including branched alkyl sulfates).

"Linear Guerbet" alcohols are available from Henkel, e.g., EUTANOL G-16.

Primary akyl sulfates derived from alcohols made by Oxo reaction onpropylene or n-butylene oligomers are described in U.S. Pat. No.5,245,072 assigned to Mobil Corp. See also: U.S. Pat. No. 5,284,989,assigned to Mobil Oil Corp. (a method for producing substantially linearhydrocarbons by oligomerizing a lower olefin at elevated temperatureswith constrained intermediate pore siliceous acidic zeolite), and U.S.Pat. Nos. 5,026,933 and 4,870,038, both to Mobil Oil Corp. (a processfor producing substantially linear hydrocarbons by oligomerizing a lowerolefin at elevated temperatures with siliceous acidic ZSM-23 zeolite).

See also: Surfactant Science Series, Marcel Dekker, N.Y. (variousvolumes include those entitled "Anionic Surfactants" and "SurfactantBiodegradation", the latter by R. D. Swisher, Second Edition, publ. 1987as Vol. 18; see especially p.20-24 "Hydrophobic groups and theirsources"; pp 28-29 "Alcohols", pp 34-35 "Primary Alkyl Sulfates" and pp35-36 "Secondary Alkyl Sulfates"); and literature on "higher" or"detergent" alcohols from which alkyl sulfates are typically made,including: CEH Marketing Research Report "Detergent Alcohols" by R. F.Modler et al., Chemical Economics Handbook, 1993, 609.5000-609.5002;Kirk Othmer's Encyclopedia of Chemical Technology, 4th Edition, Wiley,N.Y., 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 andreferences therein.

SUMMARY OF THE INVENTION

The present invention relates to surfactant compositions comprising fromabout 0.001% to about 100% of one or more (preferably a mixture of twoor more) mid-chain branched primary alkyl alkoxylated sulfates havingthe formula: ##STR5## wherein the total number of carbon atoms in thebranched primary alkyl moiety of this formula (including the R, R¹, andR² branching, but not including the carbon atoms in the EO/PO alkoxymoiety) is from 14 to 20, and wherein further for this surfactantmixture the average total number of carbon atoms in the branched primaryalkyl moieties having the above formula is within the range of greaterthan 14.5 to about 17.5 (preferably from about 15 to about 17); R, R¹,and R² are each independently selected from hydrogen and C₁ -C₃ alkyl(preferably methyl), provided R, R¹, and R² are not all hydrogen and,when z is 1, at least R or R¹ is not hydrogen; M is one or more cations;w is an integer from 0 to 13; x is an integer from 0 to 13; y is aninteger from 0 to 13; z is an integer of at least 1; w+x+y+z is from 8to 14; and EO/PO are alkoxy moieties including for example ethoxy,propoxy, butoxy, etc, preferably selected from ethoxy, propoxy, andmixed ethoxy/propoxy groups, most preferably ethoxy, wherein m is atleast about 0.01, preferably within the range of from about 0.1 to about30, more preferably from about 0.5 to about 10, and most preferably fromabout 1 to about 5. It is to be recognized that the (EO/PO)_(m) moietymay be either a distribution with average degree of alkoxylationcorresponding to m, or it may be a single specific chain withalkoxylation (e.g., ethoxylation and/or propoxylation) of exactly thenumber of units corresponding to m.

The present invention preferably further encompasses a detergentcomposition, for example one useful for laundering fabrics, washingdishes, and cleaning hard surfaces, comprising:

(a) from about 0.001% to about 99% of one or more mid-chain branchedprimary alkyl alkoxylated sulfate surfactants having the formula herein;and

(b) from about 1% to about 99.999% by weight of one or more detergentadjunct ingredients.

Preferably, said detergent compositions comprise a mixture of mid-chainbranched primary alkyl alkoxylated sulfate surfactants, said mixturecomprising at least about 5% by weight of two or more mid-chain branchedprimary alkyl alkoxylated sulfates having the formula: ##STR6## ormixtures thereof; wherein M represents one or more cations; a, b, d, ande are integers, a+b is from 10 to 16, d+e is from 8 to 14 and whereinfurther

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 8 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

wherein for this surfactant mixture the average total number of carbonatoms in the branched primary alkyl moieties having the above formulasis within the range of greater than 14.5 to about 17.5; and

wherein EO/PO are alkoxy moieties, preferably selected from ethoxy,propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about0.01, preferably within the range of from about 0.1 to about 30, morepreferably from about 0.5 to about 10, and most preferably from about 1to about 5.

It is also an object of the present invention to provide novel mid-chainbranched primary alkoxylated surfactants for use in the surfactantmixtures described herein. The invention therefore also preferablyrelates to novel alkoxylated sulfate compounds of formula: ##STR7##wherein: a is an integer from 2 to 11, b is an integer from 1 to 10, anda+b is 12 or 13; and M is selected from sodium, potassium, magnesium,ammonium and substituted ammonium, and EO/PO are alkoxy moieties,preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxygroups, wherein m is at least about 0.01, preferably within the range offrom about 0.1 to about 30, more preferably from about 0.5 to about 10,and most preferably from about 1 to about 5. More preferred embodimentsof such compounds include an alkoxylated sulfate compound of saidformula wherein M is selected from sodium, potassium and ammonium.

Also preferred herein are alkoxylated sulfate compounds of formula:##STR8## wherein: d and e are integers and d+e is 10 or 11; and whereinfurther

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

and M is selected from sodium, potassium, ammonium and substitutedammonium, more preferably sodium, potassium and ammonium, mostpreferably sodium; and EO/PO are alkoxy moieties, preferably selectedfrom ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is atleast about 0.01, preferably within the range of from about 0.1 to about30, more preferably from about 0.5 to about 10, and most preferably fromabout 1 to about 5.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (° C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to mid-chain branched primary alkylalkoxylated sulfate surfactants. The branched surfactant compositionscomprise one or more mid-chain branched primary alkyl alkoxylatedsulfate surfactants having the formula ##STR9##

The surfactant mixtures of the present invention comprise moleculeshaving a linear primary alkoxylated sulfate chain backbone (i.e., thelongest linear carbon chain which includes the alkoxy-sulfated carbonatom). These alkyl chain backbones comprise from 12 to 19 carbon atoms;and further the molecules comprise a branched primary alkyl moietyhaving at least a total of 14, but not more than 20, carbon atoms. Inaddition, the surfactant mixture has an average total number of carbonatoms for the branched primary alkyl moieties within the range of fromgreater than 14.5 to about 17.5. Thus, the present invention mixturescomprise at least one alkoxylated sulfate compound having a longestlinear carbon chain of not less than 12 carbon atoms or more than 19carbon atoms, and the total number of carbon atoms including branchingmust be at least 14, and further the average total number of carbonatoms for the branched primary alkyl chains is within the range ofgreater than 14.5 to about 17.5.

For example, a C16 total carbon (in the alkyl chain) primary alkylalkoxylated sulfate surfactant having 15 carbon atoms in the backbonemust have a methyl branching unit (either R, R¹ or R² is methyl) wherebythe total number of carbon atoms in the primary alkyl moiety of themolecule is 16.

R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃alkyl (preferably hydrogen or C₁ -C₂ alkyl, more preferably hydrogen ormethyl, and most preferably methyl), provided R, R¹, and R² are not allhydrogen. Further, when z is 1, at least R or R¹ is not hydrogen.

Although for the purposes of the present invention surfactantcompositions the above formula does not include molecules wherein theunits R, R¹, and R² are all hydrogen (i.e., linear non-branched primaryalkoxylated sulfates), it is to be recognized that the present inventioncompositions may still further comprise some amount of linear,non-branched primary alkoxylated sulfate. Further, this linearnon-branched primary alkoxylated sulfate surfactant may be present asthe result of the process used to manufacture the surfactant mixturehaving the requisite mid-chain branched primary alkoxylated sulfatesaccording to the present invention, or for purposes of formulatingdetergent compositions some amount of linear non-branched primaryalkoxylated sulfate may be admixed into the final product formulation.

It is also to be recognized that some amount of mid-chain branched alkylsulfate may be present in the compositions. This is typically the resultof sulfation of non-alkoxylated alcohol remaining following incompletealkoxylation of the mid-chain branched alcohol used to prepare thealkoxylated sulfate useful herein. It is to be recognized, however, thatseparate addition of such mid-chain branched alkyl sulfates is alsocontemplated by the present invention compositions.

Further it is to be similarly recognized that non-sulfated mid-chainbranched alcohol (including polyoxyalkylene alcohols) may comprise someamount of the present invention alkoxylated sulfate-containingcompositions. Such materials may be present as the result of incompletesulfation of the alcohol (alkoxylated or non-alkoxylated) used toprepare the alkoxylated sulfate surfactant, or these alcohols may beseparately added to the present invention detergent compositions alongwith a mid-chain branched alkoxylated sulfate surfactant according tothe present invention.

M is hydrogen or a salt forming cation depending upon the method ofsynthesis. Examples of salt forming cations are lithium, sodium,potassium, calcium, magnesium, quaternary alkyl amines having theformula ##STR10## wherein R³, R⁴, R⁵ and R⁶ are independently hydrogen,C₁ -C₂₂ alkylene, C₄ -C₂₂ branched alkylene, C₁ -C₆ alkanol, C₁ -C₂₂alkenylene, C₄ -C₂₂ branched alkenylene, and mixtures thereof. Preferredcations are ammonium (R³,R⁴, R⁵ and R⁶ equal hydrogen), sodium,potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.The monoalkanol ammonium compounds of the present invention have R³equal to C₁ -C₆ alkanol, R⁴, R⁵ and R⁶ equal to hydrogen; dialkanolammonium compounds of the present invention have R³ and R⁴ equal to C₁-C₆ alkanol, R⁵ and R⁶ equal to hydrogen; trialkanol ammonium compoundsof the present invention have R³, R⁴ and R⁵ equal to C₁ -C₆ alkanol, R⁶equal to hydrogen. Preferred alkanol ammonium salts of the presentinvention are the mono-, di- and tri- quaternary ammonium compoundshaving the formulas:

    H.sub.3 N+CH.sub.2 CH.sub.2 OH, H.sub.2 N+(CH.sub.2 CH.sub.2 OH).sub.2, HN+(CH.sub.2 CH.sub.2 OH).sub.3.

Preferred M is sodium, potassium and the C₂ alkanol ammonium saltslisted above; most preferred is sodium.

Further regarding the above formula, w is an integer from 0 to 13; x isan integer from 0 to 13; y is an integer from 0 to 13; z is an integerof at least 1; and w +x+y+z is an integer from 8 to 14.

EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, andmixed ethoxy/propoxy groups, wherein m is at least about 0.01,preferably within the range of from about 0.1 to about 30, morepreferably from about 0.5 to about 10, and most preferably from about 1to about 5. The (EO/PO)_(m) moiety may be either a distribution withaverage degree of alkoxylation (e.g., ethoxylation and/or propoxylation)corresponding to m, or it may be a single specific chain withalkoxylation (e.g., ethoxylation and/or propoxylation) of exactly thenumber of units corresponding to m.

Certain points of branching (i.e., the location along the chain of theR, R¹, and/or R² moieties in the above formula) are preferred over otherpoints of branching along the backbone of the surfactant. The formulabelow illustrates the mid-chain branching range (i.e., where points ofbranching occur), preferred mid-chain branching range, and morepreferred mid-chain branching range for mono-methyl substituted linearalkyl alkoxylated sulfates of the present invention. ##STR11## It shouldbe noted that for the mono-methyl substituted surfactants these rangesexclude the two terminal carbon atoms of the chain and the two carbonatoms immediately adjacent to the EO/PO moiety. For surfactant mixturescomprising two or more of R, R¹, or R² being other than hydrogen, alkylbranching at the 2-carbon atom is within the scope of the presentinvention surfactants. Surfactants having chains longer than ethyl (i.e.C₃ alkyl substitutents) on the 2-carbon atom, however, are lesspreferred.

The formula below illustrates the mid-chain branching range, preferredmid-chain branching range, and more preferred mid-chain branching rangefor di-methyl substituted linear alkyl alkoxylated sulfates of thepresent invention. ##STR12## When di-alkyl substituted primary alkylalkoxylated sulfates are combined with mono-substituted mid-chainbranched primary alkyl alkoxylated sulfates, the di-alkyl substitutedprimary alkoxylated sulfates having one methyl substitution on the2-carbon position and another methyl substitution in the preferred rangeas indicated above, are within the present composition surfactants.

The preferred surfactant mixtures of the present invention have at least0.001%, more preferably at least 5%, most preferably at least 20% byweight, of the mixture one or more mid-chain branched primary alkylalkoxylated sulfates having the formula ##STR13## wherein the totalnumber of carbon atoms, including branching, is from 15 to 18, andwherein further for this surfactant mixture the average total number ofcarbon atoms in the branched primary alkyl moieties having the aboveformula is within the range of greater than 14.5 to about 17.5; R¹ andR² are each independently hydrogen or C₁ -C₃ alkyl; M is a water solublecation; x is from 0 to 11; y is from 0 to 11; z is at least 2; and x+y+zis from 9 to 13; provided R¹ and R² are not both hydrogen; and EO/PO arealkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxygroups, wherein m is at least about 0.01, preferably within the range offrom about 0.1 to about 30, more preferably from about 0.5 to about 10,and most preferably from about 1 to about 5. More preferred arecompositions having at least 5% of the mixture comprising one or moremid-chain branched primary alkoxylated sulfates wherein z is at least 2.

Preferably, the mixtures of surfactant comprise at least 5%, preferablyat least about 20%, of a mid chain branched primary alkyl alkoxylatedsulfate having R¹ and R² independently hydrogen or methyl, provided R¹and R² are not both hydrogen; x+y is equal to 8, 9 or 10 and z is atleast 2.

Preferred detergent compositions according to the present invention, forexample one useful for laundering fabrics, comprise from about 0.001% toabout 99% of a mixture of mid-chain branched primary alkyl alkoxylatedsulfate surfactants, said mixture comprising at least about 5% by weightof one or more mid-chain branched alkyl alkoxylated sulfates having theformula: ##STR14## or mixtures thereof; wherein M represents one or morecations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from8 to 14 and wherein further

when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to8;

when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to9;

when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to10;

when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to11;

when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to12;

when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to13;

when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to14;

when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6;

when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7;

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to10;

when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to11;

when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to12;

and wherein further for this surfactant mixture the average total numberof carbon atoms in the branched primary alkyl moieties having the aboveformulas is within the range of greater than 14.5 to about 17.5; andEO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 0.01, preferablywithin the range of from about 0.1 to about 30, more preferably fromabout 0.5 to about 10, and most preferably from about 1 to about 5.

Further, the present invention surfactant composition may comprise amixture of branched primary alkyl alkoxylated sulfates having theformula ##STR15## wherein the total number of carbon atoms per molecule,including branching, is from 14 to 20, and wherein further for thissurfactant mixture the average total number of carbon atoms in thebranched primary alkyl moieties having the above formula is within therange of greater than 14.5 to about 17.5; R, R¹, and R² are eachindependently selected from hydrogen and C₁ -C₃ alkyl, provided R, R¹,and R² are not all hydrogen; M is a water soluble cation; w is aninteger from 0 to 13; x is an integer from 0 to 13; y is an integer from0 to 13; z is an integer of at least 1; w+x+y+z is from 8 to 14; EO/POare alkoxy moieties, preferably selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 0.01, preferablywithin the range of from about 0.1 to about 30, more preferably fromabout 0.5 to about 10, and most preferably from about 1 to about 5;provided that when R² is C₁ -C₃ alkyl the ratio of surfactants having zequal to 2 or greater to surfactants having z of 1 is at least about 1:1, preferably at least about 1.5:1, more preferably at least about 3:1,and most preferably at least about 4:1. Also preferred are surfactantcompositions when R² is C₁ -C₃ alkyl comprising less than about 50%,preferably less than about 40%, more preferably less than about 25%,most preferably less than about 20%, of branched primary alkylalkoxylated sulfate having the above formula wherein z equals 1.

The present invention further relates to novel mid-chain branchedprimary alkyl alkoxylated sulfate surfactants having the formula##STR16## wherein R¹ and R² are each independently hydrogen or C₁ -C₃alkyl; M is a water soluble cation; x is from 0 to 12; y is from 0 to12; z is at least 2; x+y+z is from 11 to 14; and EO/PO are alkoxymoieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups,wherein m is at least about 0.01, preferably within the range of fromabout 0.1 to about 30, more preferably from about 0.5 to about 10, andmost preferably from about 1 to about 5; provided R¹ and R² are not bothhydrogen.

R¹ and R² units are selected independently from hydrogen or C₁ -C₃ alkyl(preferably hydrogen or C₁ -C₂ alkyl; more preferably hydrogen ormethyl) provided R¹ and R² are not both hydrogen. M is as definedhereinbefore.

For mid-chain branched primary alkoxylated sulfates of the presentinvention having more than one alkyl branch chain, the alkyl chainbackbones comprise from 12 to 18 carbon atoms. The maximum number ofcarbons that comprise the mid-chain branched primary alkoxylatedsulfates of the present invention, including all branches, is 20 carbonatoms.

Preferred novel alkoxylated sulfate compounds have the formula:##STR17## wherein: a and b are integers and a+b is 12 or 13, a is aninteger from 2 to 11, b is an integer from 1 to 10 and M is selectedfrom sodium, potassium, ammonium and substituted ammonium, and EO/PO arealkoxy moieties, preferably selected from ethoxy, propoxy, and mixedethoxy/propoxy groups, wherein m is at least about 0.01, preferablywithin the range of from about 0.1 to about 30, more preferably fromabout 0.5 to about 10, and most preferably from about 1 to about 5. Morepreferred embodiments of such compounds include an alkoxylated sulfatecompound of said formula wherein M is selected from sodium, potassiumand ammonium.

Also preferred novel mid-chain branched primary alkyl alkoxylatedsulfate compounds have the formula: ##STR18## wherein: d and e areintegers and d+e is 10 or 11; and wherein further

when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to8;

when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to9;

and M is selected from sodium, potassium, ammonium and substitutedammonium, more preferably sodium, potassium and ammonium, mostpreferably sodium; and EO/PO are alkoxy moieties, preferably selectedfrom ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is atleast about 0.01, preferably within the range of from about 0.1 to about30, more preferably from about 0.5 to about 10, and most preferably fromabout 1 to about 5.

Preferred mono-methyl branched primary alkyl ethoxylated sulfates areselected from the group consisting of: 3-methyl pentadecanol ethoxylatedsulfate, 4-methyl pentadecanol ethoxylated sulfate, 5-methylpentadecanol ethoxylated sulfate, 6-methyl pentadecanol ethoxylatedsulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-methylpentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylatedsulfate, 10-methyl pentadecanol ethoxylated sulfate, 11-methylpentadecanol ethoxylated sulfate, 12-methyl pentadecanol ethoxylatedsulfate, 13-methyl pentadecanol ethoxylated sulfate, 3-methylhexadecanol ethoxylated sulfate, 4-methyl hexadecanol ethoxylatedsulfate, 5-methyl hexadecanol ethoxylated sulfate, 6-methyl hexadecanolethoxylated sulfate, 7-methyl hexadecanol ethoxylated sulfate, 8-methylhexadecanol ethoxylated sulfate, 9-methyl hexadecanol ethoxylatedsulfate, 10-methyl hexadecanol ethoxylated sulfate, 11-methylhexadecanol ethoxylated sulfate, 12-methyl hexadecanol ethoxylatedsulfate, 13-methyl hexadecanol ethoxylated sulfate, 14-methylhexadecanol ethoxylated sulfate, and mixtures thereof, wherein thecompounds are ethoxylated with an average degree of ethoxylation of fromabout 0.1 to about 10.

Preferred di-methyl branched primary alkyl ethoxylated sulfates selectedfrom the group consisting of: 2,3-methyl tetradecanol ethoxylatedsulfate, 2,4-methyl tetradecanol ethoxylated sulfate, 2,5-methyltetradecanol ethoxylated sulfate, 2,6-methyl tetradecanol ethoxylatedsulfate, 2,7-methyl tetradecanol ethoxylated sulfate, 2,8-methyltetradecanol ethoxylated sulfate, 2,9-methyl tetradecanol ethoxylatedsulfate, 2,10-methyl tetradecanol ethoxylated sulfate, 2,11-methyltetradecanol ethoxylated sulfate, 2,12-methyl tetradecanol ethoxylatedsulfate, 2,3-methyl pentadecanol ethoxylated sulfate, 2,4-methylpentadecanol ethoxylated sulfate, 2,5-methyl pentadecanol ethoxylatedsulfate, 2,6-methyl pentadecanol ethoxylated sulfate, 2,7-methylpentadecanol ethoxylated sulfate, 2,8-methyl pentadecanol ethoxylatedsulfate, 2,9-methyl pentadecanol ethoxylated sulfate, 2,10-methylpentadecanol ethoxylated sulfate, 2,1 1-methyl pentadecanol ethoxylatedsulfate, 2,12-methyl pentadecanol ethoxylated sulfate, 2,13-methylpentadecanol ethoxylated sulfate, and mixtures thereof, wherein thecompounds are ethoxylated with an average degree of ethoxylation of fromabout 0.1 to about 10.

Preparation of Mid-chain Branched Alkoxylated Sulfates

The following reaction scheme outlines a general approach to thepreparation of the mid-chain branched primary alcohol useful foralkoxylating and then sulfating to prepare the mid-chain branchedprimary alkyl alkoxylated sulfate surfactants of the present invention.##STR19##

An alkyl halide is converted to a Grignard reagent and the Grignard isreacted with a haloketone. After conventional acid hydrolysis,acetylation and thermal elimination of acetic acid, an intermediateolefin is produced (not shown in the scheme) which is hydrogenatedforthwith using any convenient hydrogenation catalyst such as Pd/C.

This route is favorable over others in that the branch, in thisillustration a 5-methyl branch, is introducedearly in the reactionsequence.

Formylation of the alkyl halide resulting from the first hydrogenationstep yields alcohol product, as shown in the scheme. This can bealkoxylated using standard techniques and then sulfated using anyconvenient sulfating agent, e.g., chlorosulfonic acid, SO3/air, oroleum, to yield the final branched primary alkyl alkoxylated sulfatesurfactant. There is flexibility to extend the branching one additionalcarbon beyond that which is achieved by a single formylation. Suchextension can, for example, be accomplished by reaction with ethyleneoxide. See "Grignard Reactions of Nonmetallic Substances", M. S.Kharasch and 0. Reinmuth, Prentice-Hall, N.Y., 1954; J. Org. Chem., J.Cason and W. R. Winans, Vol. 15 (1950), pp 139-147; J. Org Chem., J.Cason et al., Vol. 13 (1948), pp 239-248; J. Org Chem., J. Cason et al.,Vol. 14 (1949), pp 147-154; and J. Org Chem., J. Cason et al., Vol. 15(1950), pp 135-138 all of which are incorporated herein by reference.

In variations of the above procedure, alternate haloketones or Grignardreagents may be used. PBr3 halogenation of the alcohol from formylationor ethoxylation can be used to accomplish an iterative chain extension.

The preferred mid-chained branched primary alkyl alkoxylated sulfates ofthe present invention can also be readily prepared as follows: ##STR20##

A conventional bromoalcohol is reacted with triphenylphosphine followedby sodium hydride, suitably in dimethylsulfoxide/tetrahydrofuran, toform a Wittig adduct. The Wittig adduct is reacted with an alpha methylketone, forming an internally unsaturated methyl-branched alcoholate.Hydrogenation followed by alkoxylation and then sulfation yields thedesired mid-chain branched primary alkyl alkoxylated sulfate. Althoughthe Wittig approach does not allow the practitioner to extend thehydrocarbon chain, as in the Grignard sequence, the Wittig typicallyaffords higher yields. See Agricultural and Biological Chemistry, M.Horiike et al., vol. 42 (1978), pp 1963-1965 included herein byreference.

Any alternative synthetic procedure in accordance with the invention maybe used to prepare the branched primary alkyl alkoxylated sulfates. Themid-chain branched primary alkyl alkoxylated sulfates may, in additionbe synthesized or formulated in the presence of the conventionalhomologs, for example any of those which may be formed in an industrialprocess which produces 2-alkyl branching as a result ofhydroformylation. Mid-chain branched surfactant mixtures of the presentinvention are routinely added to other known commercial alkylalkoxylated sulfates contained in the final laundry product formulation.

In certain preferred embodiments of the surfactant mixtures of thepresent invention, especially those derived from fossil fuel sourcesinvolving commercial processes, comprise at least 1 mid-chain branchedprimary alkyl alkoxylated sulfate, preferably at least 2, morepreferably at least 5, most preferably at least 8.

Particularly suitable for preparation of certain surfactant mixtures ofthe present invention are "oxo" reactions wherein a branched chainolefin is subjected to catalytic isomerization and hydroformylationprior to alkoxylation and sulfation. The preferred processes resultingin such mixtures utilize fossil fuels as the starting materialfeedstock. Preferred processes utilize Oxo reaction on linear olefins(alpha or internal) with a limited amount of branching. Suitable olefinsmay be made by dimerization of linear alpha or internal olefins, bycontrolled oligomerization of low molecular weight linear olefins, byskeletal rearrangement of detergent range olefins, bydehydrogenation/skeletal rearrangement of detergent range paraffins, orby Fischer-Tropsch reaction. These reactions will in general becontrolled to: 1) give a large proportion of olefins in the desireddetergent range (while allowing for the addition of a carbon atom in thesubsequent Oxo reaction), 2) produce a limited number of branches,preferably mid-chain, 3) produce C₁ -C₃ branches, more preferably ethyl,most preferably methyl, 4) limit or eliminate gem dialkyl branching i.e.to avoid formation of quaternary carbon atoms. The suitable olefins canundergo Oxo reaction to give primary alcohols either directly orindirectly through the corresonding aldehydes. When an internal olefinis used, an Oxo catalyst is normally used which is capable of priorpre-isomerization of internal olefins primarily to alpha olefins. Whilea separately catalyzed (i.e. non-Oxo) internal to alpha isomerizationcould be effected, this is optional. On the other hand, if theolefin-forming step itself results directly in an alpha olefin (e.g.with high pressure Fischer-Tropsch olefins of detergent range), then useof a non-isomerizing Oxo catalyst is not only possible, but preferred.

The process described herein above gives the more preferred5-methyl-hexadecyl alkoxylated sulfate in higher yield than the lesspreferred 2,4-dimethylpentadecyl alkoxylated sulfate. This mixture isdesirable under the metes and bounds of the present invention in thateach product comprises at total of 17 carbon atoms with linear alkylchains having at least 13 carbon atoms.

The following examples provide methods for synthesizing variouscompounds useful in the present invention compositions.

EXAMPLE I Preparation of sodium 7-methylhexadecyl ethoxylated (E2)sulfate Synthesis of (6-hydroxyhexyl) triphenylphosphonium bromide

Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5L) at 10° C. Vacuumfiltration followed by washing with ethyl ether and drying in a vacuumoven at 50° C. for 2 hrs. gives 1140 g of the desired product as whitecrystals.

Synthesis of 7-methylhexadecene-1-ol

Into a dried 5L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping fimnel, thermometer and nitrogenoutlet is added 70.2 g of 60% sodium hydride (1.76 mol) in mineral oil.The mineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and the mixture is heated to70° C. until evolution of hydrogen stops. The reaction mixture is cooledto room temperature followed by addition of 1L of anhydroustetrahydrofuran. (6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g,1 mol) is slurried with warm anhydrous dimethyl sulfoxide (50° C., 500ml) and slowly added to the reaction mixture through the dropping funnelwhile keeping it at 25-30° C. The mixture is stirred for 30 minutes atroom temperature at which time 2-undecanone (187 g, 1.1 mol) is slowlyadded through a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. The mixture is stirred for 18hr. and then poured into a 5L beaker containing 1L purified water withstirring. The oil phase (top) is allowed to separate out in a separatoryfunnel and the water phase is removed. The water phase is washed withhexanes (500 ml) and the organic phase is separated and combined withthe oil phase from the water wash. The organic mixture is then extractedwith water 3 times (500 ml each) followed by vacuum distillation tocollect the clear, oily product (132 g) at 140C and 1 mm Hg.

Hydrogenation of 7-methylhexadecene-1-ol

Into a 3L rocking autoclave liner is added 7-methylhexadecene-1-ol (130g, 0.508 mol), methanol (300 ml) and platinum on carbon (10% by weight,35 g). The mixture is hydrogenated at 180° C. under 1200 psig ofhydrogen for 13 hrs., cooled and vacuum filtered thru Celite 545 withwashing of the Celite 545, suitably with methylene chloride. If needed,the filtration can be repeated to eliminate traces of Pt catalyst, andmagnesium sulfate can be used to dry the product. The solution ofproduct is concentrated on a rotary evaporator to obtain a clear oil(124 g).

Alkoxylation of 7-methylihexadecanol

Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to two equivalents of ethylene oxide) has beenadded, nitrogen is swept through the apparatus for 20-30 minutes as thesample is allowed to cool. The desired 7-methylhexadecyl ethoxylate(average of 2 ethoxylates per molecule) product is then collected.

Sulfation of 7-meth ylhexadecyl ethoxylate (E2)

Into a dried IL 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylhexadecyl ethoxylate (E2) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with an ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot ethanol (55° C.) and vacuum filtered immediately. The filtrate isconcentrated to a slurry on a rotary evaporator, cooled and then pouredinto ethyl ether. The mixture is chilled to 5° C. and vacuum filtered toprovide the desired 7-methylhexadecyl ethoxylate (average of 2ethoxylates per molecule) sulfate, sodium salt, product.

EXAMPLE II Synthesis of sodium 7-methlpentadecyl ethoxylated (E3)sulfate Synthesis of (6-hydroxyhexyl) Triphenylphosphonium Bromide

Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo- 1 -hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9mol) and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylpentadecene-1-ol

Into a dried 5L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-decanone (171.9 g, 1.1 mol) isslowly added thru a dropping funnel. Reaction is slightly exothermic andcooling is needed to maintain 25-30° C. Mixture is stirred for 18 hrs.and then poured into a separatory funnel containing 600 ml of purifiedwater and 300 ml of hexanes. After shaking the oil phase (top) isallowed to separate out and the water phase is removed. The extractionsof the oil phase are continued using water until both phases are clear.The organic phase is collected, vacuum distilled and purified by liquidchromatography (90:10 hexanes:ethyl acetate, silica gel stationaryphase) to obtain a clear, oily product (119.1 g).

Hydrogenation of 7-methylpentadecene-1-ol

Into a 3L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylpentadecene-1-ol (122 g, 0.508 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. The organic mixture is still dark from platinum catalyst sothe filtration procedure is repeated with concentration on a rotaryevaporator; dilution is carried out with methylene chloride (500 ml) andmagnesium sulfate is aded to dry product. Vacuum filter thru Celite 545and concentrate filtrate on a rotary evaporator to obtain a clear oil(119 g).

Alkoxylation of 7-methylpentadecanol

Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to three equivalents of ethylene oxide) hasbeen added, nitrogen is swept through the apparatus for 20-30 minutes asthe sample is allowed to cool. The desired 7-methylpentadecyl ethoxylate(average of 3 ethoxylates per molecule) product is then collected.

Sulfation of 7-methylpentadecyl ethoxylate (E3)

Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylpentadecyl ethoxylate (E3) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedmethanol and 1-butanol. Vacuum filter off the inorganic salt precipitateand remove methanol from the filtrate on a rotary evaporator. Cool toroom temperature, add ethyl ether and let stand for 1 hour. Theprecipitate is collected by vacuum filtration to provide the desired7-methylpentadecyl ethoxylate (average of 3 ethoxylates per molecule)sulfate, sodium salt, product.

EXAMPLE III Synthesis of sodium 7-methylheptadecyl ethoxylated (E1.5)sulfate Synthesis of (6-Hydroxyhexyl) Triphenylphosphonium bromide

Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet,condenser, thermometer, mechanical stirring and nitrogen outlet is added6-bromo-1-hexanol (500 g, 2.76 mol), triphenylphosphine (768 g, 2.9 mol)and acetonitrile (1800 ml) under nitrogen. The reaction mixture isheated to reflux for 72 hrs. The reaction mixture is cooled to roomtemperature and transferred into a 5L beaker. The product isrecrystallized from anhydrous ethyl ether (1.5L) at 10° C. Vacuumfiltration of the mixture followed by washing the white crystals withethyl ether and drying in a vacuum oven at 50° C. for 2 hrs. gives 1140g of the desired product.

Synthesis of 7-methylheptadecene-1-ol

Into a dried 5L, 3 neck round bottom flask fitted with mechanicalstirring, nitrogen inlet, dropping funnel, thermometer and nitrogenoutlet is added 80 g of 60% sodium hydride (2.0 mol) in mineral oil. Themineral oil is removed by washing with hexanes. Anhydrous dimethylsulfoxide (500 ml) is added to the flask and heated to 70° C. untilevolution of hydrogen stops. The reaction mixture is cooled to roomtemperature followed by addition of 1L of anhydrous tetrahydrofuran.(6-hydroxyhexyl) triphenylphosphonium bromide (443.4 g, 1 mol) isslurried with warm anhydrous dimethyl sulfoxide (50° C., 500 ml) andslowly added to the reaction mixture thru the dropping funnel whilekeeping the reaction at 25-30° C. The reaction is stirred for 30 minutesat room temperature at which time 2-dodecanone (184.3 g, 1.1 mol) isslowly added thru a dropping ftunnel. Reaction is slightly exothermicand cooling is needed to maintain 25-30° C. Mixture is stirred for 18hrs. and then poured into a separatory funnel containing 600 ml ofpurified water and 300 ml of hexanes. After shaking the oil phase (top)is allowed to separate out and the water phase is removed which iscloudy. The extractions are continued using water until the water phaseand the organic phase become clear. The organic phase is collected andpurified by liquid chromatography (mobile phase-hexanes, stationaryphase-silica gel ) to obtain a clear, oily product (116 g). HNMR of thefinal product (in deuterium oxide) indicates a CH₂ --OSO₃ --triplet atthe 3.8 ppm resonance, CH₂ --CH₂ --OSO₃ --multiplet at the 1.5 ppmresonance, CH₂ of the alkyl chain at the 0.9-1.3 ppm resonance andCH--CH₃ branch point overlapping the R--CH₂ CH₃ terminal methyl group atthe 0.8 ppm resonance.

Hydrogenation of 7-methylheptadecene-1-ol

Into a 3L rocking autoclave glass liner (Autoclave Engineers) is added7-Methylheptadecene-1-ol (1 16 g, 0.433 mol), methanol (300 ml) andplatinum on carbon (10% by weight, 40 g). The mixture is hydrogenated at180° C. under 1200 psig of hydrogen for 13 hrs., cooled and vacuumfiltered thru Celite 545 with washing of Celite 545 with methylenechloride. Vacuum filter thru Celite 545 and concentrate filtrate on arotary evaporator to obtain a clear oil (108 g).

Alkoxylation of 7-methylpentadecanol

Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet,mechanical stirrer, and a y-tube fitted with a thermometer and a gasoutlet is added the alcohol from the preceeding step. For purposes ofremoving trace amounts of moisture, the alcohol is sparged with nitrogenfor about 30 minutes at 80-100° C. Continuing with a nitrogen sweep,sodium metal is added as the catalyst and allowed to melt with stirringat 120-140° C. With vigorous stirring, ethylene oxide gas is added in140 minutes while keeping the reaction temperature at 120-140° C. Afterthe correct weight (equal to 1.5 equivalents of ethylene oxide) has beenadded, nitrogen is swept through the apparatus for 20-30 minutes as thesample is allowed to cool. The desired 7-methylheptadecyl ethoxylate(average of 1.5 ethoxylates per molecule) product is then collected.

Sulfation of 7-methylheptadecyl ethoxylate (E1.5)

Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet,dropping funnel, thermometer, mechanical stirring and nitrogen outlet isadded chloroform and 7-methylheptadecyl ethoxylate (E1.5) from thepreceeding step. Chlorosulfonic acid is slowly added to the stirredmixture while maintaining 25-30° C. temperature with a ice bath. OnceHCl evolution has stopped slowly add sodium methoxide (25% in methanol)while keeping temperature at 25-30° C. until a aliquot at 5%concentration in water maintains a pH of 10.5. To the mixture is addedhot methanol (45° C.) to dissolve the branched sulfate followedimmediately by vacuum filtration to remove the inorganic saltprecipitate and repeated a second time. The filtrate is then cooled to5° C. at which time ethyl ether is added and let stand for 1 hour. Theprecipitate is collected by vacuum filtration to provide the desired7-methylheptadecyl ethoxylate (average of 1.5 ethoxylates per molecule)sulfate, sodium salt, product.

EXAMPLE IV

The following Shell Research experimental test alcohol samples areethoxylated (average ethoxylation of 2.5) and then sulfated by thefollowing procedure.

    ______________________________________                                        .sup.13 C-NMR Results For Branched Alcohols Prepared                          Total Number of Carbons                                                                        16        17     18                                          ______________________________________                                        Avg. Number of Branches per                                                                    2.0       1.7    2.1                                         Molecule                                                                      Average Branch Position Relative To                                           Hydroxyl Carbon                                                               % at C4 and higher                                                                             56%       55%    52%                                         % at C3          26%       21%    25%                                         % at C2          18%       24%    23%                                         Type of Branching                                                             % propyl and higher                                                                            31%       35%    30%                                         % ethyl          12%       10%    12%                                         % methyl         57%       55%    58%                                         ______________________________________                                    

Into a dried 250 ml 3 neck round bottom flask fitted with a nitrogeninlet, mechanical stirrer, and a y-tube fitted with a thermometer and agas outlet is added the C16 alcohol (48.4 g, 0.2 mol) above. Forpurposes of removing trace amounts of moisture, the alcohol is spargedwith nitrogen for about 30 minutes at 80-100° C. Continuing with anitrogen sweep, sodium metal (0.23g, 0.01 mol) is added as the catalystand allowed to melt with stirring at 120-140° C. With vigorous stirring,ethylene oxide gas (22 g, 0.5 mol) is added in 140 minutes while keepingthe reaction temperature at 120-140° C. After the correct weight ofethylene oxide (average 2.5 ethoxylates per molecule) has been added,nitrogen is swept through the apparatus for 20-30 minutes as the sampleis allowed to cool. The gold liquid product (69 g, 0.196 mol) is bottledunder nitrogen.

Sulfation of this C16 ethoxylate utilizes the following procedure. Intoa dried 500 ml 3 neckround bottom flask fitted with a gas inlet,dropping funnel, mechanical stirrer, and a y-tube fitted with athermometer and a gas outlet is added the C16 ethoxylate from theprevious step (63.4 g, 0.18 mol) and diethyl ether (75 ml).Chlorosulfonic acid (22.1 g, 0.19 mol) is added slowly to the stirredmixture while maintaining a reaction temperature of 5-15° C. with an icewater bath. After the chlorosulfonic acid is added a slow nitrogen sweepand a vacuum (10-15 inches Hg) is begun to remove HCl. Also the reactionis warmed to 30-40° C. with the addition of a warm water bath. Afterabout 45 minutes the vacuum is increased to 25-30 inches Hg andmaintained for an additional 45 minutes. The acidic reaction mixture isslowly poured into a vigorously stirred beaker of 25% sodium methoxide(43.2 g, 0.2 mol) and methanol (200 ml) that is cooled in an ice waterbath. After pH>12 is confirmed the solution is allowed to stir about 15minutes then poured into a glass dish. Most of the solvent is allowed toevaporate overnight in the fume hood. The next morning the dish istransferred to a vacuum drying oven. The sample is allowed to dry allday and overnight at 40-60° C. with 25-30 inches Hg vacuum. Yellow tackysolid (80.9 g; 93% active) C16 ethoxylated (E2.5) sulfate, sodium salt,product is collected.

The following two analytical methods for characterizing branching in thepresent invention surfactant compositions are useful:

1) Separation and Identification of Components in Fatty Alcohols (priorto alkoxylation or after hydrolysis of alcohol alkoxy sulfate foranalytical purposes). The position and length of branching found in theprecursor fatty alcohol materials is determined by GC/MS techniques[see: D. J. Harvey, Biomed, Environ. Mass Spectrom (1989). 18(9),719-23; D. J. Harvey, J. M. Tiffany, J. Chromatogr. (1984), 301(1),173-87; K. A. Karlsson, B. E. Samuelsson, G. O. Steen, Chem. Phys.Lipids (1973), 11(1), 17-38].

2) Identification of Separated Fatty Alcohol Alkoxy Sulfate Componentsby MS/MS. The position and length of branching is also determinable byIon Spray-MS/MS or FAB-MS/MS techniques on previously isolated fattyalcohol alkoxy sulfate components.

The average total carbon atoms of the branched primary alkyl sulfatesherein can be calculated from the hydroxyl value of the precursor fattyalcohol mix or from the hydroxyl value of the alcohols recovered byextraction after hydrolysis of the alcohol alkoxy sulfate mix accordingto common procedures, such as outlined in "Bailey's Industrial Oil andFat Products", Volume 2, Fourth Edition, edited by Daniel Swern, pp.440-441.

INDUSTRIAL APPLICABILITY

Branched-chain primary alkoxylated sulfate surfactants of the typeherein can be used in all manner of cleaning compositions. The detergentcompositions of the invention thus may also contain additional detergentcomponents. The precise nature of these additional components, andlevels of incorporation thereof will depend on the physical form of thecomposition, and the precise nature of the cleaning operation for whichit is to be used. The longer-chain derivatives are more soluble thanexpected and the shorter-chain derivatives clean better than expected.Cleaning compositions herein include, but are not limited to: granular,bar-form and liquid laundry detergents; liquid hand dishwashingcompositions; liquid, gel and bar-form personal cleansing products;shampoos; dentifrices; hard surface cleaners, and the like. Suchcompositions can contain a variety of conventional detersiveingredients.

The following listing of such ingredients is for the convenience of theformulator, and not by way of limitation of the types of ingredientswhich can be used with the branched-chain surfactants herein. Thecompositions of the invention preferably contain one or more additionaldetergent components selected from surfactants, builders, alkalinitysystem, organic polymeric compounds, suds suppressors, soil suspensionand anti-redeposition agents and corrosion inhibitors.

Bleaching Compounds--Bleaching Agents and Bleach Activators--Thedetergent compositions herein preferably further contain bleachingagents or bleaching compositions containing a bleaching agent and one ormore bleach activators. Bleaching agents will typically be at levels offrom about 1% to about 30%, more typically from about 5% to about 20%,of the detergent composition, especially for fabric laundering. Ifpresent, the amount of bleach activators will typically be from about0.1% to about 60%, more typically from about 0.5% to about 40% of thebleaching composition comprising the bleaching agent-plus-bleachactivator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patent application740,446, Bums et al, filed Jun. 3, 1985, European Patent Application0,133,354, Banks et al, published Feb. 20, 1985, and U.S. Pat. No.4,412,934, Chung et al, issued Nov. 1, 1983. Highly preferred bleachingagents also include 6-nonylamino-6-oxoperoxycaproic acid as described inU.S. Pat. No. 4,634,551, issued Jan. 6, 1987 to Bums et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators, which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamido-caproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR21##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR22## wherein R⁶ is H or an alkyl, aryl,alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.Highly preferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. No. 5,246,621, U.S. Pat. No. No. 5,244,594; U.S. Pat. No.5,194,416; U.S. Pat. No. 5,114,606; and European Pat. App. Pub. Nos.549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples ofthese catalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ -(PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄) ₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc) ₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use ofmanganese with various complex ligands to enhance bleaching is alsoreported in the following United States Patents: U.S. Pat. Nos.4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes",Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferredcobalt catalyst useful herein are cobalt pentaamine acetate salts havingthe formula [Co(NH₃)₅ OAc] T_(y), wherein "OAc" represents an acetatemoiety and "T_(y) " is an anion, and especially cobalt pentaamineacetate chloride, [Co(NH₃)₅ OAc]Cl₂ ; as well as [Co(NH₃)₅ OAc](OAc)₂ ;[Co(NH₃)₅ OAc](PF₆)₂ ; [Co(NH₃)₅ OAc](SO₄); [Co(NH₃)₅ OAc](BF₄)₂ ; and[Co(NH₃)₅ OAc](NO₃)₂ (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article and the references cited therein,in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7,1989, J.Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterizationof Inorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem, 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

Enzymes--Enzymes are preferably included in the present detergentcompositions for a variety of purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates, for the prevention of refugee dye transfer in fabriclaundering, and for fabric restoration. Suitable enzymes includeproteases, amylases, lipases, cellulases, peroxidases, and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition. Preferred detersiveenzymes are hydrolases such as proteases, amylases and lipases.Preferred enzymes for laundry purposes include, but are not limited to,proteases, cellulases, lipases and peroxidases. Highly preferred forautomatic dishwashing are amylases and/or proteases, including bothcurrent commercially available types and improved types which, thoughmore and more bleach compatible though successive improvements, have aremaining degree of bleach deactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a "cleaning-effectiveamount". The term "cleaning effective amount" refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics, dishware and the like. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically 0.01 mg to 3 mg, of active enzyme per gram of thedetergent composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition. For certaindetergents, such as in automatic dishwashing, it may be desirable toincrease the active enzyme content of the commercial preparation inorder to minimize the total amount of non-catalytically active materialsand thereby improve spotting/filming or other end-results. Higher activelevels may also be desirable in highly concentrated detergentformulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble . When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as"Protease D" is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein, especially for, but not limited to automaticdishwashing purposes, include, for example, α-amylases described in GB1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. andTERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineeringof enzymes for improved stability, e.g., oxidative stability, is known.See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp.6518-6521. Certain preferred embodiments of the present compositions canmake use of amylases having improved stability in detergents such asautomatic dishwashing types, especially improved oxidative stability asmeasured against a reference-point of TERMAMY® in commercial use in1993. These preferred amylases herein share the characteristic of being"stability-enhanced" amylases, characterized, at a minimum, by ameasurable improvement in one or more of: oxidative stability, e.g., tohydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH9-10; thermal stability, e.g., at common wash temperatures such as about60° C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled "Oxidatively Resistant alpha-Amylases" presented at the207th American Chemical Society National Meeting, Mar. 13-17 1994, by C.Mitchinson. Therein it was noted that bleaches in automatic dishwashingdetergents inactivate alpha-amylases but that improved oxidativestability amylases have been made by Genencor from B. licheniformisNCIB8061. Methionine (Met) was identified as the most likely residue tobe modified. Met was substituted, one at a time, in positions 8, 15,197, 256, 304, 366 and 438 leading to specific mutants, particularlyimportant being M197L and M197T with the M197T variant being the moststable expressed variant. Stability was measured in CASCADE® andSUNLIGHT®; (c) particularly preferred amylases herein include amylasevariants having additional modification in the immediate parent asdescribed in WO 9510603 A and are available from the assignee, Novo, asDURAMYL®. Other particularly preferred oxidative stability enhancedamylase include those described in WO 9418314 to Genencor Internationaland WO 9402597 to Novo. Any other oxidative stability-enhanced amylasecan be used, for example as derived by site-directed mutagenesis fromknown chimeric, hybrid or simple mutant parent forms of availableamylases. Other preferred enzyme modifications are accessible. See WO9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and inco-pending application by Novo Nordisk PCT/DK96/00056. Specific amylaseenzymes for use in the detergent compositions of the present inventioninclude α-amylases characterized by having a specific activity at least25% higher than the specific activity of Termamyl® at a temperaturerange of 25° C. to 55° C. and at a pH value in the range of 8 to 10,measured by the Phadebas® α-amylase activity assay. (Such Phadebas®α-amylase activity assay is described at pages 9-10, WO 95/26397.) Alsoincluded herein are α-amylases which are at least 80% homologous withthe amino acid sequences shown in the SEQ ID listings in the references.These enzymes are preferably incorporated into laundry detergentcompositions at a level from 0.00018% to 0.060% pure enzyme by weight ofthe total composition, more preferably from 0.00024% to 0.048% pureenzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fingal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fimgus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," or "Amano-P." Other suitable commerciallipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only thelipase derived from Humicola lanuginosa and produced in Aspergillusoryzae as host has so far found widespread application as additive forfabric washing products. It is available from Novo Nordisk under thetradename Lipolase™, as noted above. In order to optimize the stainremoval performance of Lipolase, Novo Nordisk have made a number ofvariants. As described in WO 92/05249, the D96L variant of the nativeHumicola lanuginosa lipase improves the lard stain removal efficiency bya factor 4.4 over the wild-type lipase (enzymes compared in an amountranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No.35944 published on Mar. 10, 1994, by Novo Nordisk discloses that thelipase variant (D96L) may be added in an amount corresponding to0.001-100-mg (5-500,000 LU/liter) lipase variant per liter of washliquor. The present invention provides the benefit of improved whitenessmaintenance on fabrics using low levels of D96L variant in detergentcompositions containing the mid-chain branched primary alkyl alkoxylatedsulfate surfactants in the manner disclosed herein, especially when theD96L is used at levels in the range of about 50 LU to about 8500 LU perliter of wash solution.

Cutinase enzymes suitable for use herein are described in WO 8809367 Ato Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g.,percarbonate, perborate, hydrogen peroxide, etc., for "solutionbleaching" or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981. Enzymes for use in detergents can be stabilised by varioustechniques. Enzyme stabilisation techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilisationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Enzyme Stabilizing System--The enzyme-containing compositions herein mayoptionally also comprise from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, most preferably from about 0.01% to about 6%,by weight of an enzyme stabilizing system. The enzyme stabilizing systemcan be any stabilizing system which is compatible with the detersiveenzyme. Such a system may be inherently provided by other formulationactives, or be added separately, e.g., by the formulator or by amanufacturer of detergent-ready enzymes. Such stabilizing systems can,for example, comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acids, boronic acids, and mixtures thereof, and aredesigned to address different stabilization problems depending on thetype and physical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calciumand/or magnesium ions in the finished compositions which provide suchions to the enzymes. Calcium ions are generally more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used. Typi compositions, especially liquids, will comprise fromabout 1 to about 30, preferably from about 2 to about 20, morepreferably from about 8 to about 12 millimoles of calcium ion per literof finished detergent composition, though variation is possibledepending on factors including the multiplicity, type and levels ofenzymes incorporated. Preferably water-soluble calcium or magnesiumsalts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium maleate, calciumhydroxide and calcium acetate; more generally, calcium sulfate ormagnesium salts corresponding to the exemplified calcium salts may beused. Further increased levels of Calcium and/or Magnesium may of coursebe useful, for example for promoting the grease-cutting action ofcertain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson,U.S. Pat. No. 4,537,706. Borate stabilizers, when used, may be at levelsof up to 10% or more of the composition though moi e typically, levelsof up to about 3% by weight of boric acid or other borate compounds suchas borax or orthoborate are suitable for liquid detergent use.Substituted boric acids such as phenylboronic acid, butaneboronic acid,p-bromophenylboronic acid or the like can be used in place of boric acidand reduced levels of total boron in detergent compositions may bepossible though the use of such substituted boron derivatives.

Stabilizing systems of certain cleaning compositions, for exampleautomatic dishwashing compositions, may firther comprise from 0 to about10%, preferably from about 0.01% to about 6% by weight, of chlorinebleach scavengers, added to prevent chlorine bleach species present inmany water supplies from attacking and inactivating the enzymes,especially under alkaline conditions. While chlorine levels in water maybe small, typically in the range from about 0.5 ppm to about 1.75 ppm,the available chlorine in the total volume of water that comes incontact with the enzyme, for example during dish- or fabric-washing, canbe relatively large; accordingly, enzyme stability to chlorine in-use issometimes problematic. Since perborate or percarbonate, which have theability to react with chlorine bleach, may present in certain of theinstant compositions in amounts accounted for separately from thestabilizing system, the use of additional stabilizers against chlorine,may, most generally, not be essential, though improved results may beobtainable from their use. Suitable chlorine scavenger anions are widelyknown and readily available, and, if used, can be salts containingammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate,iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organicamines such as ethylenediaminetetracetic acid (EDTA) or alkali metalsalt thereof, monoethanolamine (MEA), and mixtures thereof can likewisebe used. Likewise, special enzyme inhibition systems can be incorporatedsuch that different enzymes have maximum compatibility. Otherconventional scavengers such as bisulfate, nitrate, chloride, sources ofhydrogen peroxide such as sodium perborate tetrahydrate, sodiumperborate monohydrate and sodium percarbonate, as well as phosphate,condensed phosphate, acetate, benzoate, citrate, formate, lactate,malate, tartrate, salicylate, etc., and mixtures thereof can be used ifdesired. In general, since the chlorine scavenger finction can beperformed by ingredients separately listed under better recognizedfunctions, (e.g., hydrogen peroxide sources), there is no absoluterequirement to add a separate chlorine scavenger unless a compoundperforming that finction to the desired extent is absent from anenzyme-containing embodiment of the invention; even then, the scavengeris added only for optimum results. Moreover, the formulator willexercise a chemist's normal skill in avoiding the use of any enzymescavenger or stabilizer which is majorly incompatible, as formulated,with other reactive ingredients. In relation to the use of ammoniumsalts, such salts can be simply admixed with the detergent compositionbut are prone to adsorb water and/or liberate ammonia during storage.Accordingly, such materials, if present, are desirably protected in aparticle such as that described in U.S. Pat. No. 4,652,392, Baginski etal.

Builders--Detergent builders selected from aluminosilicates andsilicates are preferably included in the compositions herein, forexample to assist in controlling mineral, especially Ca and/or Mg,hardness in wash water or to assist in the removal of particulate soilsfrom surfaces.

Suitable silicate builders include water-soluble and hydrous solid typesand including those having chain-, layer-, or three-dimensional-structure as well as amorphous-solid or non-structured-liquid types.Preferred are alkali metal silicates, particularly those liquids andsolids having a SiO₂ :Na₂ O ratio in the range 1.6:1 to 3.2:1,including, particularly for automatic dishwashing purposes, solidhydrous 2-ratio silicates marketed by PQ Corp. under the tradenameBRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., thosedescribed in U.S. Pat. No. 4,664,839, May 12, 1987, H. P. Rieck.NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layeredaluminium-free δ-Na₂ SiO₅ morphology silicate marketed by Hoechst and ispreferred especially in granular laundry compositions. See preparativemethods in German DE-A-3,417,649 and DE-A-3,742,043. Other layeredsilicates, such as those having the general formula NaMSi_(x)O_(2x+1).yH₂ O wherein M is sodium or hydrogen, x is a number from 1.9to 4, preferably 2, and y is a number from 0 to 20, preferably 0, canalso or alternately be used herein. Layered silicates from Hoechst alsoinclude NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γ layer-silicateforms. Other silicates may also be useful, such as magnesium silicate,which can serve as a crispening agent in granules, as a stabilisingagent for bleaches, and as a component of suds control systems.

Also suitable for use herein are synthesized crystalline ion exchangematerials or hydrates thereof having chain structure and a compositionrepresented by the following general formula in an anhydride form: xM₂O.ySiO₂.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to2.0 and z/x is 0.005 to 1.0 as taught in U.S. Pat. No. 5,427,711,Sakaguchi et al, Jun. 27, 1995.

Aluminosilicate builders are especially useful in granular detergents,but can also be incorporated in liquids, pastes or gels. Suitable forthe present purposes are those having empirical formula: [M_(z)(AlO₂)_(z) (SiO₂)_(v) ].xH₂ O wherein z and v are integers of at least6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x isan integer from 15 to 264. Aluminosilicates can be crystalline oramorphous, naturally-occurring or synthetically derived. Analuminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP. Natural types, includingclinoptilolite, may be used. Zeolite A has the formula: Na₁₂ [(AlO₂)₁₂(SiO₂)₁₂ ].xH₂ O wherein x is from 20 to 30, especially 27. Dehydratedzeolites (x=0-10) may also be used. Preferably, the aluminosilicate hasa particle size of 0.1-10 microns in diameter.

Detergent builders in place of or in addition to the silicates andaluminosilicates described hereinbefore can optionally be included inthe compositions herein, for example to assist in controlling mineral,especially Ca and/or Mg, hardness in wash water or to assist in theremoval of particulate soils from surfaces. Builders can operate via avariety of mechanisms including forming soluble or insoluble complexeswith hardness ions, by ion exchange, and by offering a surface morefavorable to the precipitation of hardness ions than are the surfaces ofarticles to be cleaned. Builder level can vary widely depending upon enduse and physical form of the composition. Built detergents typicallycomprise at least about 1% builder. Liquid formulations typicallycomprise about 5% to about 50%, more typically 5% to 35% of builder.Granular formulations typically comprise from about 10% to about 80%,more typically 15% to 50% builder by weight of the detergentcomposition. Lower or higher levels of builders are not excluded. Forexample, certain detergent additive or high-surfactant formulations canbe unbuilt.

Suitable builders herein can be selected from the group consisting ofphosphates and polyphosphates, especially the sodium salts; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates especially water-soluble nonsurfactant carboxylates inacid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing detergent compositions.

Builder mixtures, sometimes termed "builder systems" can be used andtypically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein. In terms of relative quantities ofsurfactant and builder in the present detergents, preferred buildersystems are typically formulated at a weight ratio of surfactant tobuilder of from about 60:1 to about 1:80. Certain preferred laundrydetergents have said ratio in the range 0.90:1.0 to 4.0:1.0, morepreferably from 0.95:1.0 to 3.0:1.0.

P-containing detergent builders often preferred where permitted bylegislation include, but are not limited to, the alkali metal, ammoniumand alkanolammonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

Suitable carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973, although sodium bicarbonate, sodiumcarbonate, sodium sesquicarbonate, and other carbonate minerals such astrona or any convenient multiple salts of sodium carbonate and calciumcarbonate such as those having the composition 2Na₂ CO₃.CaCO₃ whenanhydrous, and even calcium carbonates including calcite, aragonite andvaterite, especially forms having high surface areas relative to compactcalcite may be useful, for example as seeds or for use in syntheticdetergent bars.

Suitable organic detergent builders include polycarboxylate compounds,including water-soluble nonsurfactant dicarboxylates andtricarboxylates. More typically builder polycarboxylates have aplurality of carboxylate groups, preferably at least 3 carboxylates.Carboxylate builders can be formulated in acid, partially neutral,neutral or overbased form. When in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.Polycarboxylate builders include the ether polycarboxylates, such asoxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, Jan. 18, 1972; "TMS/TDS"builders of U.S. Pat. No. 4,663,071, Bush et al, May 5, 1987; and otherether carboxylates including cyclic and alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1,3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid;carboxymethyloxysuccinic acid; the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxy-methyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are importantcarboxylate builders e.g., for heavy duty liquid detergents, due toavailability from renewable resources and biodegradability. Citrates canalso be used in granular compositions, especially in combination withzeolite and/or layered silicates. Oxydisuccinates are also especiallyuseful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used forhand-laundering operations, alkali metal phosphates such as sodiumtripolyphosphates, sodium pyrophosphate and sodium orthophosphate can beused. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonateand other known phosphonates, e.g., those of U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and mayhave desirable antiscaling properties.

Certain detersive surfactants or their short-chain homologs also have abuilder action. For unambiguous formula accounting purposes, when theyhave surfactant capability, these materials are summed up as detersivesurfactants. Preferred types for builder functionality are illustratedby: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acidbuilders include the C₅ -C₂₀ alkyl and alkenyl succinic acids and saltsthereof. Succinate builders also include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Lauryl-succinates are describedin European Patent Application 86200690.5/0,200,263, published Nov. 5,1986. Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions as surfactant/builder materials aloneor in combination with the aforementioned builders, especially citrateand/or the succinate builders, to provide additional builder activity.Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Other types of inorganic builder materials which can be used have theformula (M_(x))_(i) Ca_(y) (CO₃)_(z) wherein x and i are integers from 1to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Miare cations, at least one of which is a water-soluble, and the equationΣ_(i=1-15) (x_(i) multiplied by the valence of M_(i))+2y=2z is satisfiedsuch that the formula has a neutral or "balanced" charge. These buildersare referred to herein as "Mineral Builders". Waters of hydration oranions other than carbonate may be added provided that the overallcharge is balanced or neutral. The charge or valence effects of suchanions should be added to the right side of the above equation.Preferably, there is present a water-soluble cation selected from thegroup consisting of hydrogen, water-soluble metals, hydrogen, boron,ammonium, silicon, and mixtures thereof, more preferably, sodium,potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium andpotassium being highly preferred. Nonlimiting examples of noncarbonateanions include those selected from the group consisting of chloride,sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate,nitrate, borate and mixtures thereof. Preferred builders of this type intheir simplest forms are selected from the group consisting of Na₂Ca(CO₃)₂, K₂ Ca(CO₃)₂, Na₂ Ca₂ (CO₃)₃, NaKCa(CO₃)₂, NaKCa₂ (CO₃)₃, K₂Ca₂ (CO₃)₃, and combinations thereof. An especially preferred materialfor the builder described herein is Na₂ Ca(CO₃)₂ in any of itscrystalline modifications. Suitable builders of the above-defined typeare further illustrated by, and include, the natural or synthetic formsof any one or combinations of the following minerals: Afghanite,Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite,Cancrinite, Carbocemaite, Carletonite, Davyne, DonnayiteY, Fairchildite,Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite,Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite,LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite,Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite,Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite,Vishnevite, and Zemkorite. Preferred mineral forms include Nyererite,Fairchildite and Shortite.

Detersive Surfactants:

The detergent compositions according to the present invention preferablyfurther comprise additional surfactants, herein also referred to asco-surfactants. It is to be understood that the branched-chainsurfactants prepared in the manner of the present invention may be usedsingly in cleaning compositions or in combination with other detersivesurfactants. Typically, fully-formulated cleaning compositions willcontain a mixture of surfactant types in order to obtain broad-scalecleaning performance over a variety of soils and stains and under avariety of usage conditions. One advantage of the branched-chainsurfactants herein is their ability to be readily formulated incombination with other known surfactant types. Nonlimiting examples ofadditional surfactants which may be used herein typically at levels fromabout 1% to about 55%, by weight, include the unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates ("AE_(x) S";especially EO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxy carboxylates(especially the EO 1-5 ethoxycarboxylates), the C₁₀ -C₁₈ glycerol ethersulfates, the C₁₀ -C₁₈ alkyl polyglycosides and their correspondingsulfated polyglycosides, and C₁₂ -C₁₈ alpha-sulfonated fatty acidesters. Nonionic surfactants such as the ethoxylated C₁₀ -C₁₈ alcoholsand alkyl phenols, (e.g., C₁₀ -C₁₈ EO (1-10) can also be used. Ifdesired, other conventional surfactants such as the C₁₂ -C₁₈ betainesand sulfobetaines ("sultaines"), CIO-C₁₈ amine oxides, and the like, canalso be included in the overall compositions. The CIO-C₁₈ N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples includethe C₁₂ -C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such asC₁₀ -C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀ -C₂₀ conventional soapsmay also be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆ soaps may be used. C₁₀ -C₁₄ alkyl benzene sulfonates (LAS), whichare often used in laundry detergent compositions, can also be used withthe branched surfactants herein.

A wide range of these co-surfactants can be used in the detergentcompositions of the present invention. A typical listing of anionic,nonionic, ampholytic and zwitterionic classes, and species of theseco-surfactants, is given in U.S. Pat. No. 3,664,961 issued to Norris onMay 23, 1972. Amphoteric surfactants are also described in detail in"Amphoteric Surfactants, Second Edition", E. G. Lomax, Editor (published1996, by Marcel Dekker, Inc.)

The laundry detergent compositions of the present invention typicallycomprise from about 0.1% to about 35%, preferably from about 0.5% toabout 15%, by weight of co-surfactants. Selected co-surfactants arefurther identified as follows.

(1) Anionic Co-surfactants

Nonlimiting examples of anionic co-surfactants useful herein, typicallyat levels from about 0.1% to about 50%, by weight, include theconventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") and primary,branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), the C₁₀ -C₁₈secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x) (CHOSO₃ ⁻M⁺) CH₃ and CH₃ (CH₂)_(y) (CHOSO₃ ⁻ M⁺) CH₂ CH₃ where x and (y+1) areintegers of at least about 7, preferably at least about 9, and M is awater-solubilizing cation, especially sodium, unsaturated sulfates suchas oleyl sulfate, the C₁₀ -C₁₈ alpha-sulfonated fatty acid esters, theC₁₀ -C₁₈ sulfated alkyl polyglycosides, the C₁₀ -C₁₈ alkyl alkoxysulfates ("AE_(x) S"; especially EO 1-7 ethoxy sulfates), and C₁₀ -C₁₈alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates).The C₁₂ -C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀ -C₁₈ amineoxides, and the like, can also be included in the overall compositions.C₁₀ -C₂₀ conventional soaps may also be used. If high sudsing isdesired, the branched-chain C₁₀ -C₁₆ soaps may be used. Otherconventional useful anionic co-surfactants are listed in standard texts.

The alkyl alkoxy sulfate surfactants useful herein are preferably watersoluble salts or acids of the formula RO(A)mSO3M wherein R is anunsubstituted C₁₀ -C₂₄ alkyl or hydroxyalkyl group having a C₁₀ -C₂₄alkyl component, preferably a C₁₂ -C₁₈ alkyl or hydroxyalkyl, morepreferably C₁₂ -C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxyunit, m is greater than zero, typically between about 0.5 and about 6,more preferably between about 0.5 and about 3, and M is H or a cationwhich can be, for example, a metal cation (e.g., sodium, potassium,lithium, calcium, magnesium, etc.), ammonium or substituted-ammoniumcation. Alkyl ethoxylated sulfates as well as alkyl propoxylatedsulfates are contemplated herein. Specific examples of substitutedammonium cations include ethanol-, triethanol-, methyl-, dimethyl,trimethyl-ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and those derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine,mixtures thereof, and the like. Exemplary surfactants are C₁₂ -C₁₅ alkylpolyethoxylate (1.0) sulfate (C₁₂ -C₁₅ E(1.0)M), C₁₂ -C₁₅ alkylpolyethoxylate (2.25) sulfate (C₁₂ -C₁₅ E(2.25)M), C₁₂ -C₁₅ alkylpolyethoxylate (3.0) sulfate (C₁₂ -C₁₅ E(3.0)M), and C₁₂ -C₁₅ alkylpolyethoxylate (4.0) sulfate (C₁₂ -C₁₅ E(4.0)M), wherein M isconveniently selected from sodium and potassium.

The alkyl sulfate surfactants useful herein are preferably water solublesalts or acids of the formula ROS0₃ M wherein R preferably is a C₁₀ -C₂₄hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀ -C₁₈ alkylcomponent, more preferably a C₁₂ -C₁₅ alkyl or hydroxyalkyl, and M is Hor a cation, e.g., an alkali metal cation (e.g. sodium, potassium,lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-,and trimethyl ammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and quaternaryammonium cations derived from alkylamines such as ethylamine,diethylamine, triethylamine, and mixtures thereof, and the like).

Other suitable anionic surfactants that can be used are alkyl estersulfonate surfactants including linear esters of C₈ -C₂₀ carboxylicacids (i.e., fatty acids) which are sulfonated with gaseous S03according to "The Journal of the American Oil Chemists Society", 52(1975), pp. 323-329. Suitable starting materials would include naturalfatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundryapplications, comprise alkyl ester sulfonate surfactants of thestructural formula:

    R.sup.3 --CH(SO.sub.3 M)--C(O)--OR.sup.4

wherein R³ is a C₈ -C₂₀ hydrocarbyl, preferably an alkyl, or combinationthereof, R⁴ is a C₁ -C₆ hydrocarbyl, preferably an alkyl, or combinationthereof, and M is a cation which forms a water soluble salt with thealkyl ester sulfonate. Suitable salt-forming cations include metals suchas sodium, potassium, and lithium, and substituted or unsubstitutedammonium cations, such as monoethanolamine, diethanolamine, andtriethanolamine. Preferably, R³ is C₁₀ -C₁₆ alkyl, and R⁴ is methyl,ethyl or isopropyl. Especially preferred are the methyl ester sulfonateswherein R³ is C₁₀ -C₁₆ alkyl.

Other anionic co-surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di- andtriethanolamine salts) of soap, C₈ -C₂₂ primary of secondaryalkanesulfonates, C₈ -C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈ -C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂ -C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆ -C₁₂ diesters), sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), and alkylpolyethoxy carboxylates such as those of the formula RO(CH2CH₂ O)_(k)--CH₂ COO--M+ wherein R is a C₈ -C₂₂ alkyl, k is an integer from 0 to10, and M is a soluble salt-forming cation. Resin acids and hydrogenatedresin acids are also suitable, such as rosin, hydrogenated rosin, andresin acids and hydrogenated resin acids present in or derived from talloil. Further examples are described in "Surface Active Agents andDetergents" (Vol. I and II by Schwartz, Perry and Berch). A variety ofsuch surfactants are also generally disclosed in U.S. Pat. No.3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line58 through Column 29, line 23 (herein incorporated by reference).

A preferred disulfate surfactant has the formula ##STR23## where R is analkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine oramide group of chain length C₁ to C₂₈, preferably C₃ to C₂₄, mostpreferably C₈ to C₂₀, or hydrogen; A and B are independently selectedfrom alkyl, substituted alkyl, and alkenyl groups of chain length C₁ toC₂₈, preferably C₁ to C₅, most preferably C₁ or C₂, or a covalent bond,and A and B in total contain at least 2 atoms; A, B, and R in totalcontain from 4 to about 31 carbon atoms; X and Y are anionic groupsselected from the group consisting of sulfate and sulfonate, providedthat at least one of X or Y is a sulfate group; and M is a cationicmoiety, preferably a substituted or unsubstituted ammonium ion, or analkali or alkaline earth metal ion.

The most preferred disulfate surfactant has the formula as above where Ris an alkyl group of chain length from C₁₀ to C₁₈, A and B areindependently C₁ or C₂, both X and Y are sulfate groups, and M is apotassium, ammonium, or a sodium ion.

The disulfate surfactant is typically present at levels of incorporationof from about 0.1% to about 50%, preferably from about 0.1% to about35%, most preferably from about 0.5% to about 15% by weight of thedetergent composition.

Preferred disulfate surfactant herein include:

(a) 1,3 disulfate compounds, preferably 1,3 C7-C23 (i.e., the totalnumber of carbons in the molecule) straight or branched chain alkyl oralkenyl disulfates, more preferably having the formula: ##STR24##wherein R is a straight or branched chain alkyl or alkenyl group ofchain length from about C₄ to about C₁₈ ;

(b) 1,4 disulfate compounds, preferably 1,4 C8-C22 straight or branchedchain alkyl or alkenyl disulfates, more preferably having the formula:##STR25## wherein R is a straight or branched chain alkyl or alkenylgroup of chain length from about C₄ to about C₁₈ ; preferred R areselected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl,octadecyl, and mixtures thereof; and

(c) 1,5 disulfate compounds, preferably 1,5 C9-C23 straight or branchedchain alkyl or alkenyl disulfates, more preferably having the formula:##STR26## wherein R is a straight or branched chain alkyl or alkenylgroup of chain length from about C₄ to about C₁₈.

Known syntheses of certain disulfated surfactants, in general, use analkyl or alkenyl succinic anhydride as the principal starting material.This is initially subjected to a reduction step from which a diol isobtained. Subsequently the diol is subjected to a sulfation step to givethe disulfated product. As an example, U.S. Pat. No. 3,634,269 describes2-alkyl or alkenyl-1,4-butanediol disulfates prepared by the reductionof alkenyl succinic anhydrides with lithium aluminium hydride to produceeither alkenyl or alkyl diols which are then sulfated. In addition, U.S.Pat. No. 3,959,334 and U.S. Pat. No. 4,000,081 describe2-hydrocarbyl-1,4-butanediol disulfates also prepared using a methodinvolving the reduction of alkenyl succinic anhydrides with lithiumaluminium hydride to produce either alkenyl or alkyl diols which arethen sulfated.

See also U.S. Pat. No. 3,832,408 and U.S. Pat. No. 3,860,625 whichdescribe 2-alkyl or alkenyl-1,4-butanediol ethoxylate disulfatesprepared by the reduction of alkenyl succinic anhydrides with lithiumaluminium hydride to produce either alkenyl or alkyl diols which arethen ethoxylated prior to sulfation.

These compounds may also be made by a method invodisulfate surfactantfrodisulfate surfactant from a substituted cyclic anhydride having onechain substituents having in total at least 5 carbon atoms comprisingthe following steps:

(i) reduction of said substituted cyclic anhydride to form a diol; and

(ii) sulfation of said diol to form a disulfate wherein said reductionstep comprises hydrogenation under pressure in the presence of atransition metal-containing hydrogenation catalyst.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 0.1% to about 50%, preferablyfrom about 1% to about 40% by weight of an anionic surfactant.

(2) Nonionic Co-surfactants

Nonlimiting examples of nonionic co-surfactants useful herein typicallyat levels from about 0.1% to about 50%, by weight include thealkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acidamides (PFAA's), alkyl polyglycosides (APG's), C₁₀ -C₁₈ glycerol ethers,and the like.

More specifically, the condensation products of primary and secondaryaliphatic alcohols with from about 1 to about 25 moles of ethylene oxide(AE) are suitable for use as the nonionic surfactant in the presentinvention. The alkyl chain of the aliphatic alcohol can either bestraight or branched, primary or secondary, and generally contains fromabout 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, more preferably from about 10 to about 18 carbonatoms, with from about 1 to about 10 moles, preferably 2 to 7, mostpreferably 2 to 5, of ethylene oxide per mole of alcohol. Especiallypreferred nonionic surfactants of this type are the C₉ -C₁₅ primaryalcohol ethoxylates containing 3-12 moles of ethylene oxide per mole ofalcohol, particularly the C₁₂ -C₁₅ primary alcohols containing 5-10moles of ethylene oxide per mole of alcohol.

Examples of commercially available nonionic surfactants of this typeinclude: Tergitol™ 15-S-9 (the condensation product of C₁₁ -C₁₅ linearalcohol with 9 moles ethylene oxide) and Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂ -C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (thecondensation product of C₁₂ -C₁₃ linear alcohol with 3 moles of ethyleneoxide), Neodol™ 45-7 (the condensation product of C₁₄ -C₁₅ linearalcohol with 7 moles of ethylene oxide) and Neodol™ 45-5 (thecondensation product of C₁₄ -C₁₅ linear alcohol with 5 moles of ethyleneoxide) marketed by Shell Chemical Company; Kyro™ EOB (the condensationproduct of C₁₃ -C₁₅ alcohol with 9 moles ethylene oxide), marketed byThe Procter & Gamble Company; and Genapol LA 030 or 050 (thecondensation product of C₁₂ -C₁₄ alcohol with 3 or 5 moles of ethyleneoxide) marketed by Hoechst. The preferred range of HLB in these AEnonionic surfactants is from 8-17 and most preferred from 8-14.Condensates with propylene oxide and butylene oxides may also be used.

Another class of preferred nonionic co-surfactants for use herein arethe polyhydroxy fatty acid amide surfactants of the formula. ##STR27##wherein R¹ is H, or C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propylor a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction. Typical examplesinclude the C₁₂ -C₁₈ and C₁₂ -C₁₄ N-methylglucamides. See U.S. Pat. Nos.5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can alsobe used; see U.S. Pat. No. 5,489,393.

Also useful as a nonionic co-surfactant in the present invention are thealkylpolysaccharides such as those disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, having a hydrophobic group containingfrom about 6 to about 30 carbon atoms, preferably from about 10 to about16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilicgroup containing from about 1.3 to about 10, preferably from about 1.3to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties (optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside). The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6-positions on the precedingsaccharide units.

Preferred alkylpolyglycosides have the formula

    R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.Compounds of this type and their use in detergent are disclosed in EP-B0 070 077, 0 075 996 and 0 094 118.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles, morepreferably from about 3 to about 15 moles, of ethylene oxide per mole ofalkyl phenol. Commercially available nonionic surfactants of this typeinclude Igepal™ CO-630, marketed by the GAF Corporation; and Triton™X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.These surfactants are commonly referred to as alkylphenol alkoxylates(e.g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol arealso suitable for use as the additional nonionic surfactant in thepresent invention. The hydrophobic portion of these compounds willpreferably have a molecular weight of from about 1500 to about 1800 andwill exhibit water insolubility. The addition of polyoxyethylenemoieties to this hydrophobic portion tends to increase the watersolubility of the molecule as a whole, and the liquid character of theproduct is retained up to the point where the polyoxyethylene content isabout 50% of the total weight of the condensation product, whichcorresponds to condensation with up to about 40 moles of ethylene oxide.Examples of compounds of this type include certain of thecommercially-available Pluronic™ surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionicsurfactant system of the present invention, are the condensationproducts of ethylene oxide with the product resulting from the reactionof propylene oxide and ethylenediamine. The hydrophobic moiety of theseproducts consists of the reaction product of ethylenediamine and excesspropylene oxide, and generally has a molecular weight of from about 2500to about 3000. This hydrophobic moiety is condensed with ethylene oxideto the extent that the condensation product contains from about 40% toabout 80% by weight of polyoxyethylene and has a molecular weight offrom about 5,000 to about 11,000. Examples of this type of nonionicsurfactant include certain of the commercially available Tetronic™compounds, marketed by BASF.

Also preferred nonionics are amine oxide surfactants. The compositionsof the present invention may comprise amine oxide in accordance with thegeneral formula I:

    R.sup.1 (EO).sub.x (PO).sub.y (BO).sub.z N(O)(CH.sub.2 R').sub.2.q H.sub.2 O(I).

In general, it can be seen that the structure (I) provides onelong-chain moiety R¹ (EO)_(x) (PO)_(y) (BO)_(z) and two short chainmoieties, CH₂ R'. R' is preferably selected from hydrogen, methyl and--CH₂ OH. In general R¹ is a primary or branched hydrocarbyl moietywhich can be saturated or unsaturated, preferably, R¹ is a primary alkylmoiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having chainlength offrom about 8 to about 18. When x+y+z is different from 0, R¹ may besomewhat longer, having a chainlength in the range C₁₂ -C₂₄. The generalformula also encompasses amine oxides wherein x+y+z=0, R₁ =C₈ -C₁₈, R'=Hand q=0-2, preferably 2. These amine oxides are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamineoxide and their hydrates, especially the dihydrates as disclosed in U.S.Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.

The invention also encompasses amine oxides wherein x+y+z is differentfrom zero, specifically x+y+z is from about 1 to about 10, R¹ is aprimary alkyl group containing 8 to about 24 carbons, preferably fromabout 12 to about 16 carbon atoms; in these embodiments y+z ispreferably 0 and x is preferably from about 1 to about 6, morepreferably from about 2 to about 4; EO represents ethyleneoxy; POrepresents propyleneoxy; and BO represents butyleneoxy. Such amineoxides can be prepared by conventional synthetic methods, e.g., by thereaction of alkylethoxysulfates with dimethylamine followed by oxidationof the ethoxylated amine with hydrogen peroxide.

Highly preferred amine oxides herein are solutions at ambienttemperature. Amine oxides suitable for use herein are made commerciallyby a number of suppliers, including Akzo Chemie, Ethyl Corp., andProcter & Gamble. See McCutcheon's compilation and Kirk-Othmer reviewarticle for alternate amine oxide manufacturers.

Whereas in certain of the preferred embodiments R' is H, there is somelatitude with respect to having R' slightly larger than H. Specifically,the invention further encompasses embodiments wherein R' is CH₂ OH, suchas hexadecylbis(2-hydroxyethyl)amine oxide,tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amineoxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamineoxide dihydrate.

(3) Cationic Co-surfactants

Nonlimiting examples of cationic co-surfactants useful herein typicallyat levels from about 0.1% to about 50%, by weight include the cholineester-type quats and alkoxylated quaternary ammonium (AQA) surfactantcompounds, and the like.

Cationic co-surfactants useful as a component of the surfactant systemis a cationic choline ester-type quat surfactant which are preferablywater dispersible compounds having surfactant properties and comprise atleast one ester (i.e. --COO--) linkage and at least one cationicallycharged group. Suitable cationic ester surfactants, including cholineester surfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

Preferred cationic ester surfactants are those having the formula:##STR28## wherein R₁ is a C₅ -C₃₁ linear or branched alkyl, alkenyl oralkaryl chain or M⁻ .N⁺ (R₆ R₇ R₈)(CH₂)_(s) ; X and Y, independently,are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH,NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO,OCOO, OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇ and R₈ are independentlyselected from the group consisting of alkyl, alkenyl, hydroxyalkyl,hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms; andR₅ is independently H or a C₁ -C₃ alkyl group; wherein the values of m,n, s and t independently lie in the range of from 0 to 8, the value of blies in the range from 0 to 20, and the values of a, u and vindependently are either 0 or 1 with the proviso that at least one of uor v must be 1; and wherein M is a counter anion.

Preferably R₂, R₃ and R₄ are independently selected from CH₃ and --CH₂CH₂ OH.

Preferably M is selected from the group consisting of halide, methylsulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,bromide or iodide.

Preferred water dispersible cationic ester surfactants are the cholineesters having the formula: ##STR29## wherein R₁ is a C₁₁ -C₁₉ linear orbranched alkyl chain.

Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (R¹ =C₁₇ alkyl),palmitoyl choline ester quaternary methylammonium halides (R¹ =C₁₅alkyl), myristoyl choline ester quaternary methylammonium halides (R¹=C₁₃ alkyl), lauroyl choline ester quaternary methylammonium halides (R¹=C₁₁ alkyl), cocoyl choline ester quaternary methylammonium halides (R¹=C₁₁ -C₁₃ alkyl), tallowyl choline ester quaternary methylammoniumhalides (R¹ =C₁₅ -C₁₇ alkyl), and any mixtures thereof.

The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain lengthwith dimethylaminoethanol, in the presence of an acid catalyst. Thereaction product is then quaternized with a methyl halide, preferably inthe presence of a solvent such as ethanol, propylene glycol orpreferably a fatty alcohol ethoxylate such as C₁₀ -C₁₈ fatty alcoholethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groupsper mole forming the desired cationic material. They may also beprepared by the direct esterification of a long chain fatty acid of thedesired chain length together with 2-haloethanol, in the presence of anacid catalyst material. The reaction product is then quatemized withtrimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulasbelow, wherein d may be from 0 to 20. ##STR30## In a preferred aspectthese cationic ester surfactant are hydrolysable under the conditions ofa laundry wash method.

Cationic co-surfactants useful herein also include alkoxylatedquaternary ammonium (AQA) surfactant compounds (referred to hereinafteras "AQA compounds") having the formula: ##STR31## wherein R¹ is a linearor branched alkyl or alkenyl moiety containing from about 8 to about 18carbon atoms, preferably 10 to about 16 carbon atoms, most preferablyfrom about 10 to about 14 carbon atoms; R² is an alkyl group containingfrom one to three carbon atoms, preferably methyl; R³ and R⁴ can varyindependently and are selected from hydrogen (preferred), methyl andethyl; X⁻ is an anion such as chloride, bromide, methylsulfate, sulfate,or the like, sufficient to provide electrical neutrality. A and A' canvary independently and are each selected from C₁ -C₄ alkoxy, especiallyethoxy (i.e., --CH₂ CH₂ O--), propoxy, butoxy and mixed ethoxy/propoxy;p is from 0 to about 30, preferably 1 to about 4 and q is from 0 toabout 30, preferably 1 to about 4, and most preferably to about 4;preferably both p and q are 1. See also: EP 2,084, published May 30,1979, by The Procter & Gamble Company, which describes cationicco-surfactants of this type which are also useful herein.

AQA compounds wherein the hydrocarbyl substituent R¹ is C₈ -C₁₁,especially C₁₀, enhance the rate of dissolution of laundry granules,especially under cold water conditions, as compared with the higherchain length materials. Accordingly, the C₈ -C₁₁ AQA surfactants may bepreferred by some formulators. The levels of the AQA surfactants used toprepare finished laundry detergent compositions can range from about0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.

According to the foregoing, the following are nonlimiting, specificillustrations of AQA surfactants used herein. It is to be understoodthat the degree of alkoxylation noted herein for the AQA surfactants isreported as an average, following common practice for conventionalethoxylated nonionic surfactants. This is because the ethoxylationreactions typically yield mixtures of materials with differing degreesof ethoxylation. Thus, it is not uncommon to report total EO valuesother than as whole numbers, e.g., "EO2.5", "EO3.5", and the like.

    ______________________________________                                        Designation R.sup.1 R.sup.2  ApR.sup.3                                                                              A'qR.sup.4                              ______________________________________                                        AQA-1       C.sub.12 -C.sub.14                                                                    CH.sub.3 EO       EO                                      (also referred to as                                                          Coco Methyl EO2)                                                              AQA-2       C.sub.12 -C.sub.16                                                                    CH.sub.3 (EO).sub.2                                                                             EO                                      AQA-3       C.sub.12 -C.sub.14                                                                    CH.sub.3 (EO).sub.2                                                                             (EO).sub.2                              (Coco Methyl EO4)                                                             AQA-4       C.sub.12                                                                              CH.sub.3 EO       EO                                      AQA-5       C.sub.12 -C.sub.14                                                                    CH.sub.3 (EO).sub.2                                                                             (EO).sub.3                              AQA-6       C.sub.12 -C.sub.14                                                                    CH.sub.3 (EO).sub.2                                                                             (EO).sub.3                              AQA-7       C.sub.8 -C.sub.18                                                                     CH.sub.3 (EO).sub.3                                                                             (EO).sub.2                              AQA-8       C.sub.12 -C.sub.14                                                                    CH.sub.3 (EO).sub.4                                                                             (EO).sub.4                              AQA-9       C.sub.12 -C.sub.14                                                                    C.sub.2 H.sub.5                                                                        (EO).sub.3                                                                             (EO).sub.3                              AQA-10      C.sub.12 -C.sub.18                                                                    C.sub.3 H.sub.7                                                                        (EO).sub.3                                                                             (EO).sub.4                              AQA-11      C.sub.12 -C.sub.18                                                                    CH.sub.3 (propoxy)                                                                              (EO).sub.3                              AQA-12      C.sub.10 -C.sub.18                                                                    C.sub.2 H.sub.5                                                                        (iso-propoxy).sub.2                                                                    (EO).sub.3                              AQA-13      C.sub.10 -C.sub.18                                                                    CH.sub.3 (EO/PO).sub.2                                                                          (EO).sub.3                              AQA-14      C.sub.8 -C.sub.18                                                                     CH.sub.3 (EO).sub.15 *                                                                          (EO).sub.15 *                           AQA-15      C.sub.10                                                                              CH.sub.3 EO       EO                                      AQA-16      C.sub.8 -C.sub.12                                                                     CH.sub.3 EO       EO                                      AQA-17      C.sub.9 -C.sub.11                                                                     CH.sub.3                                                  EO 3.5 Avg. -                                                                 AQA-18      C.sub.12                                                                              CH.sub.3                                                  EO 3.5 Avg. -                                                                 AQA-19      C.sub.8 -C.sub.14                                                                     CH.sub.3 (EO).sub.10                                                                            (EO).sub.10                             AQA-20      C.sub.10                                                                              C.sub.2 H.sub.5                                                                        (EO).sub.2                                                                             (EO).sub.3                              AQA-21      C.sub.12 -C.sub.14                                                                    C.sub.2 H.sub.5                                                                        (EO).sub.5                                                                             (EO).sub.3                              AQA-22      C.sub.12 -C.sub.18                                                                    C.sub.3 H.sub.7                                                                        Bu       (EO)2                                   ______________________________________                                         *Ethoxy, optionally endcapped with methyl or ethyl.                      

The preferred bis-ethoxylated cationic surfactants herein are availableunder the trade name ETHOQUAD from Akzo Nobel Chemicals Company.

Highly preferred bis-AQA compounds for use herein are of the formula##STR32## wherein R¹ is C₁₀ -C₁₈ hydrocarbyl and mixtures thereof,preferably C₁₀, C₁₂, C₁₄ alkyl and mixtures thereof, and X is anyconvenient anion to provide charge balance, preferably chloride. Withreference to the general AQA structure noted above, since in a preferredcompound R¹ is derived from coconut (C₁₂ -C₁₄ alkyl) fraction fattyacids, R² is methyl and ApR³ and A'qR⁴ are each monoethoxy, thispreferred type of compound is referred to herein as "CocoMeEO2" or"AQA-1" in the above list.

Other preferred AQA compounds herein include compounds of the formula:##STR33## wherein R¹ is C₁₀ -C₁₈ hydrocarbyl, preferably C₁₀ -C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁ -C₃alkyl, preferably methyl, and X is an anion, especially chloride.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂ CH₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy[CH(CH₃)CH₂ O] and [CH₂ CH(CH₃ O] units (i-Pr) or n-propoxy units (Pr),or mixtures of EO and/or Pr and/or i-Pr units.

The following illustrates various other adjunct ingredients which may beused in the compositions of this invention, but is not intended to belimiting thereof. While the combination of the mid-chain branchedprimary alkyl alkoxylated sulfate surfactants with such adjunctcompositional ingredients can be provided as finished products in theform of liquids, gels, bars, or the like using conventional techniques,the manufacture of the granular laundry detergents herein requires somespecial processing techniques in order to achieve optimal performance.Accordingly, the manufacture of laundry granules will be describedhereinafter separately in the Granules Manufacture section (below), forthe convenience of the formulator.

Additional cationic co-surfactants are described, for example, in the"Surfactant Science Series, Volume 4, Cationic Surfactants" or in the"Industrial Surfactants Handbook". Classes of useful cationicsurfactants described in these references include amide quats (i.e.,Lexquat AMG & Schercoquat CAS), glycidyl ether quats (i.e., Cyostat609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e.,Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammoniumcompounds (i.e., pyridinium or imidazolinium quats), and/or benzalkoniumquats.

Polymeric Soil Release Agent--Known polymeric soil release agents,hereinafter "SRA" or "SRA's", can optionally be employed in the presentdetergent compositions. If utilized, SRA's will generally comprise from0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0%by weight, of the composition.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles therebyserving as an anchor for the hydrophilic segments. This can enablestains occurring subsequent to treatment with SRA to be more easilycleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cationic(see U.S. Pat. No. 4,956,447), as well as noncharged monomer units andstructures may be linear, branched or even star-shaped. They may includecapping moieties which are especially effective in controlling molecularweight or altering the physical or surface-active properties. Structuresand charge distributions may be tailored for application to differentfiber or textile types and for varied detergent or detergent additiveproducts.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without of course forming adensely crosslinked overall structure.

Suitable SRA's include: a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink: such ester oligomers can be prepared by(a) ethoxylating allyl alcohol, (b) reacting the product of (a) withdimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in atwo-stage transesterification/ oligomerization procedure and (c)reacting the product of (b) with sodium metabisulfite in water; thenonionic end-capped 1,2-propylene/polyoxyethylene terephthalatepolyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al,for example those produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)("PEG"); the partly- and fuilly- anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol ("EG"), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, Me-capped PEG and EG and/orPG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al, the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT optionally but preferably flurther comprising addedPEG, e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide m terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; and the C₁ -C₄ alkylcelluloses and C₄ hydroxyalkylcelluloses; see U.S. Pat. No. 4,000,093, December 28, 1976 to Nicol, etal. Suitable SRA's characterised by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkyleneoxide backbones. See European Patent Application 0 219 048, publishedApr. 22, 1987 by Kud, et al. Commercially available examples includeSOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. OtherSRA's are polyesters with repeat units containing 10-15% by weight ofethylene terephthalate together with 90-80% by weight of polyoxyethyleneterephthalate, derived from a polyoxyethylene glycol of averagemolecular weight 300-5,000. Commercial examples include ZELCON 5126 fromDupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula (CAP)₂(EG/PG)₅ (T)₅ (SIP)₁ which comprises terephthaloyl (T),sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG)units and which is preferably terminated with end-caps (CAP), preferablymodified isethionates, as in an oligomer comprising onesulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy andoxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 toabout 10:1, and two end-cap units derived from sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA preferably furthercomprises from 0.5% to 20%, by weight of the oligomer, of acrystallinity-reducing stabiliser, for example an anionic surfactantsuch as linear sodium dodecylbenzenesulfonate or a member selected fromxylene-, cumene-, and toluene- sulfonates or mixtures thereof, thesestabilizers or modifiers being introduced into the synthesis pot, all astaught in U.S. Pat. No. 5,415,807, Gosselink, Pan, Kellett and Hall,issued May 16, 1995. Suitable monomers for the above SRA include Na2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na- dimethyl5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising:(1) a backbone comprising (a) at least one unit selected from the groupconsisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit whichis at least trifinctional whereby ester linkages are formed resulting ina branched oligomer backbone, and combinations thereof; (b) at least oneunit which is a terephthaloyl moiety; and (c) at least one unsulfonatedunit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more cappingunits selected from nonionic capping units, anionic capping units suchas alkoxylated, preferably ethoxylated, isethionates, alkoxylatedpropanesulfonates, alkoxylated propanedisulfonates, alkoxylatedphenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferredof such esters are those of empirical formula:

    {(CAP)x(EG/PG)y'(DEG)y"(PEG)y'"(T)z(SIP)z'(SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG)represents di(oxyethylene)oxy units; (SEG) represents units derived fromthe sulfoethyl ether of glycerin and related moiety units; (B)represents branching units which are at least trifinctional wherebyester linkages are formed resulting in a branched oligomer backbone; xis from about 1 to about 12; y' is from about 0.5 to about 25; y" isfrom 0 to about 12; y'" is from 0 to about 10; y'+y"+y'" totals fromabout 0.5 to about 25; z is from about 1.5 to about 25; z' is from 0 toabout 12; z +z' totals from about 1.5 to about 25; q is from about 0.05to about 12; m is from about 0.01 to about 10; and x, y', y", y'", z,z', q and m represent the average number of moles of the correspondingunits per mole of said ester and said ester has a molecular weightranging from about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters includeNa-2-(2-,3-dihydroxypropoxy)ethanesulfonate ("SEG"),Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and itshomologs and mixtures thereof and the products of ethoxylating andsulfonating allyl alcohol. Preferred SRA esters in this class includethe product of transesterifying and oligomerizing sodium2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]ethanesulfonate, DMT, sodium2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using anappropriate Ti(IV) catalyst and can be designated as(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+--O₃ S[CH₂ CH₂O]3.5)-- and B is a unit from glycerin and the mole ratio EG/PG is about1.7:1 as measured by conventional gas chromatography after completehydrolysis.

Additional classes of SRA's include (I) nonionic terephthalates usingdiisocyanate coupling agents to link up polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al; (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.; (III) anionic terephthalate-based SRA'sof the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland etal; (IV) poly(vinyl caprolactam) and related co-polymers with monomerssuch as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate,including both nonionic and cationic polymers, see U.S. Pat. No.4,579,681, Ruppert et al.; (V) graft copolymers, in addition to theSOKALAN types from BASF made, by grafting acrylic monomers on tosulfonated polyesters; these SRA's assertedly have soil release andanti-redeposition activity similar to known cellulose ethers: see EP279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomerssuch as acrylic acid and vinyl acetate on to proteins such as caseins,see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA'sprepared by condensing adipic acid, caprolactam, and polyethyleneglycol, especially for treating polyamide fabrics, see Bevan et al, DE2,335,044 to Unilever N. V., 1974. Other useful SRA's are described inU.S. Pat. Nos. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay Soil Removal/Anti-redeposition Agents--The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylates amines; liquid detergent compositions typically containabout 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylenepentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents--Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other umaleic/acrylic/vinyl alcohclude themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener--Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.01% to about 1.2%, by weight, into the detergent compositionsherein. Commercial optical brighteners which may be useful in thepresent invention can be classified into subgroups, which include, butare not necessarily limited to, derivatives of stilbene, pyrazoline,coumarin, carboxylic acid, methinecyanines,dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ringheterocycles, and other miscellaneous agents. Examples of suchbrighteners are disclosed in "The Production and Application ofFluorescent Brightening Agents", M. Zahradnik, Published by John Wiley &Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on December 13, 1988. These brighteners include the PHORWHITEseries of brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; andthe amino-coumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho[1,2-d]oxazole; and2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton.

Dye Transfer Inhibiting Agents--The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR34## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modem Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol ("PEG")having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula: ##STR35## wherein R₁ is selectedfrom anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ is selectedfrom N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-forming cation such as sodium orpotassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the detergent compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory, it is believed that such brighteners work this waybecause they have high affinity for fabrics in the wash solution andtherefore deposit relatively quick on these fabrics. The extent to whichbrighteners deposit on fabrics in the wash solution can be defined by aparameter called the "exhaustion coefficient". The exhaustioncoefficient is in general as the ratio of a) the brightener materialdeposited on fabric to b) the initial brightener concentration in thewash liquor. Brighteners with relatively high exhaustion coefficientsare the most suitable for inhibiting dye transfer in the context of thepresent invention.

Of course, it will be appreciated that other, conventional opticalbrightener types of compounds can optionally be used in the presentcompositions to provide conventional fabric "brightness" benefits,rather than a true dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Chelating Agents--The detergent compositions herein may also optionallycontain one or more iron and/or manganese chelating agents. Suchchelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfinctionally-substituted aromaticchelating agents and mixtures therein, all as hereinafter defined.Without intending to be bound by theory, it is believed that the benefitof these materials is due in part to their exceptional ability to removeiron and manganese ions from washing solutions by formation of solublechelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Suds Suppressors--Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present invention.Suds suppression can be of particular importance in the so-called "highconcentration cleaning process" as described in U.S. Pat. Nos. 4,489,455and 4,489,574 and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout -40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term "paraffin," as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight % of said silicone udssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. Nos. 4,978,471,Starch, issued Dec. 18, 1990, and 4,983,316, Starch, issued Jan. 8,1991, 5,288,431, Huber et al., issued Feb. 22, 1994, and U.S. Pat. Nos.4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 throughcolumn 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a "suds suppressing amount. By "suds suppressing amount" is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 10% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Alkoxylated Polycarboxylates--Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are useful herein to provide additionalgrease removal performance. Such materials are described in WO 91/08281and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.Chemically, these materials comprise polyacrylates having one ethoxyside-chain per every 7-8 acrylate units. The side-chains are of theformula--(CH₂ CH₂ O)_(m) (CH₂)_(n) CH₃ wherein m is 2-3 and n is 6-12.The side-chains are ester-linked to the polyacrylate "backbone" toprovide a "comb" polymer type structure. The molecular weight can vary,but is typically in the range of about 2000 to about 50,000. Suchalkoxylated polycarboxylates can comprise from about 0.05% to about 10%,by weight, of the compositions herein.

Fabric Softeners--Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for example, in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

Perfumes--Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Several perfume formulations are set forth in Example XXI, hereinafter.Non-limiting examples of perfume ingredients useful herein include:7-acetyl -1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetra-methylnaphtho [2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisalde-hyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Other Ingredients--A wide variety of other ingredients useful indetergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀ -C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀ -C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.If desired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄ and the like, can be added at levels of, typically,0.1%-2%, to provide additional suds and to enhance grease removalperformance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysth, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be "protected" for use in detergents,including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

Form of the Compositions

The compositions in accordance with the invention can take a variety ofphysical forms including granular, tablet, bar and liquid forms. Thecompositions are particularly the so-called concentrated granulardetergent compositions adapted to be added to a washing machine by meansof a dispensing device placed in the machine drum with the soiled fabricload.

The mean particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.7 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

The bulk density of granular detergent compositions in accordance withthe present invention typically have a bulk density of at least 600g/litre, more preferably from 650 g/litre to 1200 g/litre.Bulk densityis measured by means of a simple finnel and cup device consisting of aconical frmnel moulded rigidly on a base and provided with a flap valveat its lower extremity to allow the contents of the funnel to be emptiedinto an axially aligned cylindrical cup disposed below the funnel. Thefunnel is 130 mm high and has internal diameters of 130 mm and 40 mm atits respective upper and lower extremities. It is mounted so that thelower extremity is 140 mm above the upper surface of the base. The cuphas an overall height of 90 mm, an internal height of 87 mm and aninternal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powder removedfrom the cup by passing a straight edged implement eg; a knife, acrossits upper edge. The filled cup is then weighed and the value obtainedfor the weight of powder doubled to provide a bulk density in g/litre.Replicate measurements are made as required.

Mid-Chain Branched Primary Alkyl Alkoxylated Sulfate AgglomerateParticles

The mid-chain branched primary alkyl alkoxylated sulfate system hereinis preferably present in granular compositions in the form of mid-chainbranched primary alkyl alkoxylated sulfate agglomerate particles, whichmay take the form of flakes, prills, marumes, noodles, ribbons, butpreferably take the form of granules. The most preferred way to processthe particles is by agglomerating powders (e.g. aluminosilicate,carbonate) with high active mid-chain branched primary alkyl alkoxylatedsulfate pastes and to control the particle size of the resultantagglomerates within specified limits. Such a process involves mixing aneffective amount of powder with a high active mid-chain branched primaryalkyl alkoxylated sulfate paste in one or more agglomerators such as apan agglomerator, a Z-blade mixer or more preferably an in-line mixersuch as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferablya high shear mixer is used, such as a Lodige CB (Trade Name).

A high active mid-chain branched primary alkyl alkoxylated sulfate pastecomprising from 50% by weight to 95% by weight, preferably 70% by weightto 85% by weight of mid-chain branched primary alkyl alkoxylated sulfateis typically used. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the surfactants used. An operating temperatureof the paste of 50° C. to 80° C. is typical.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is meant from 20 g to 300 g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65litres, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

As noted, the mid-chain branched primary alkyl alkoxylated sulfatesurfactants are used herein in detergent compositions, preferably incombination with other detersive surfactants, at levels which areeffective for achieving at least a directional improvement in cleaningperformance. In the context of a fabric laundry composition, such "usagelevels" can vary depending not only on the type and severity of thesoils and stains, but also on the wash water temperature, the volume ofwash water and the type of washing machine.

For example, in a top-loading, vertical axis U.S.-type automatic washingmachine using about 45 to 83 liters of water in the wash bath, a washcycle of about 10 to about 14 minutes and a wash water temperature ofabout 10° C. to about 50° C., it is preferred to include from about 2ppm to about 625 ppm, preferably from about 2 ppm to about 550 ppm, morepreferably from about 10 ppm to about 235 ppm, of the mid-chain branchedprimary alkyl alkoxylated sulfate surfactant in the wash liquor. On thebasis of usage rates of from about 50 ml to about 150 ml per wash load,this translates into an in-product concentration (wt.) of the mid-chainbranched primary alkyl alkoxylated sulfate surfactant of from about 0.1%to about 40%, preferably about 0.1% to about 35%, more preferably fromabout 0.5% to about 15%, for a heavy-duty liquid laundry detergent. Onthe basis of usage rates of from about 30g to about 950 g per wash load,for dense ("compact") granular laundry detergents (density above about650 g/l) this translates into an in-product concentration (wt.) of themid-chain branched primary alkyl alkoxylated sulfate surfactant of fromabout 0.1% to about 50%, preferably from about 0.1% to about 35%, andmore preferably from about 0.5% to about 15%. On the basis of usagerates of from about 80 g to about 100 g per load for spray-driedgranules (i.e., "fluffy"; density below about 650 g/l), this translatesinto an in-product concentration (wt.) of the mid-chain branched primaryalkyl alkoxylated sulfate surfactant of from about 0.07% to about 35%,preferably from about 0.07 to about 25%, and more preferably from about0.35% to about 11%.

For example, in a front-loading, horizontal-axis European-type automaticwashing machine using about 8 to 15 liters of water in the wash bath, awash cycle of about 10 to about 60 minutes and a wash water temperatureof about 30° C. to about 95° C., it is preferred to include from about 3ppm to about 14,000 ppm, preferably from about 3 ppm to about 10,000ppm, more preferably from about 15 ppm to about 4200 ppm, of themid-chain branched primary alkyl alkoxylated sulfate surfactant in thewash liquor. On the basis of usage rates of from about 45 ml to about270 ml per wash load, this translates into an in-product concentration(wt.) of the mid-chain branched primary alkyl alkoxylated sulfatesurfactant of from about 0.1% to about 50%, preferably about 0.1% toabout 35%, more preferably from about 0.5% to about 15%, for aheavy-duty liquid laundry detergent. On the basis of usage rates of fromabout 40 g to about 210 g per wash load, for dense ("compact") granularlaundry detergents (density above about 650 g/l) this translates into anin-product concentration (wt.) of the mid-chain branched primary alkylalkoxylated sulfate surfactant of from about 0.12% to about 53%,preferably from about 0.12% to about 46%, and more preferably from about0.6% to about 20%. On the basis of usage rates of from about 140 g toabout 400 g per load for spray-dried granules (i.e., "fluffy"; densitybelow about 650 g/l), this translates into an in-product concentration(wt.) of the mid-chain branched primary alkyl alkoxylated sulfatesurfactant of from about 0.03% to about 34%, preferably from about 0.03%to about 24%, and more preferably from about 0.15% to about 10%.

For example, in a top-loading, vertical-axis Japanese-type automaticwashing machine using about 26 to 52 liters of water in the wash bath, awash cycle of about 8 to about 15 minutes and a wash water temperatureof about 5° C. to about 25° C., it is preferred to include from about0.67 ppm to about 270 ppm, preferably from about 0.67 ppm to about 236ppm, more preferably from about 3.4 ppm to about 100 ppm, of themid-chain branched primary alkyl alkoxylated sulfate surfactant in thewash liquor. On the basis of usage rates of from about 20 ml to about 30ml per wash load, this translates into an in-product concentration (wt.)of the mid-chain branched primary alkyl alkoxylated sulfate surfactantof from about 0.1% to about 40%, preferably about 0.1% to about 35%,more preferably from about 0.5% to about 15%, for a heavy-duty liquidlaundry detergent. On the basis of usage rates of from about 18 g toabout 35 g per wash load, for dense ("compact") granular laundrydetergents (density above about 650 g/l) this translates into anin-product concentration (wt.) of the mid-chain branched primary alkylalkoxylated sulfate surfactant of from about 0.1% to about 50%,preferably from about 0.1% to about 35%, and more preferably from about0.5% to about 15%. On the basis of usage rates of from about 30 g toabout 40 g per load for spray-dried granules (i.e., "fluffy"; densitybelow about 650 g/l), this translates into an in-product concentration(wt.) of the mid-chain branched primary alkyl alkoxylated sulfatesurfactant of from about 0.06% to about 44%, preferably from about 0.06%to about 30%, and more preferably from about 0.3% to about 13%.

As can be seen from the foregoing, the amount of mid-chain branchedprimary alkyl alkoxylated sulfate surfactant used in a machine-washlaundering context can vary, depending on the habits and practices ofthe user, the type of washing machine, and the like. In this context,however, one heretofore unappreciated advantage of the mid-chainbranched primary alkyl alkoxylated sulfate surfactants is their abilityto provide at least directional improvements in performance over aspectrum of soils and stains even when used at relatively low levelswith respect to the other surfactants (generally anionics oranionic/nonionic mixtures) in the finished compositions.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

To allow for release of the detergent product during the wash the devicemay possess a number of openings through which the product may pass.Alternatively, the device may be made of a material which is permeableto liquid but impermeable to the solid product, which will allow releaseof dissolved product. Preferably, the detergent product will be rapidlyreleased at the start of the wash cycle thereby providing transientlocalised high concentrations of product in the drum of the washingmachine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a waythat container integrity is maintained in both the dry state and duringthe wash cycle. Especially preferred dispensing devices for use with thecomposition of the invention have been described in the followingpatents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345and EP-A-0288346. An article by J. Bland published in ManufacturingChemist, November 1989, pages 41-46 also describes especially preferreddispensing devices for use with granular laundry products which are of atype commonly know as the "granulette". Another preferred dispensingdevice for use with the compositions of this invention is disclosed inPCT Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a flexible sheath in the form of a bagextending from a support ring defining an orifice, the orifice beingadapted to admit to the bag sufficient product for one washing cycle ina washing process. A portion of the washing medium flows through theorifice into the bag, dissolves the product, and the solution thenpasses outwardly through the orifice into the washing medium. Thesupport ring is provided with a masking arrangernt to prevent egress ofwetted, undissolved, product, this arrangement typically comprisingradially extending walls extending from a central boss iin whicked wheelconfiguration, or a similar structure in which the walls have a helicalform.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 litres,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

In the following Examples, the abbreviations for the various ingredientsused for the compositions have the following meanings.

    ______________________________________                                        LAS       Sodium linear C.sub.12 alkyl benzene sulfonate                      MBAE.sub.X S.sub.Z                                                                      Mid-chain branched primary alkyl (average total                               carbons = z) ethoxylate (average EO = x) sulfate,                             sodium salt                                                         LMFAA     C12-14 alkyl N-methyl glucamide                                     APA       C8-C10 amido propyl dimethyl amine                                  Fatty Acid                                                                              C12-C14 fatty acid                                                  (C12/14)                                                                      Fatty Acid (TPK)                                                                        Topped palm kernel fatty acid                                       Fatty Acid (RPS)                                                                        Rapeseed fatty acid                                                 Borax     Na tetraborate decahydrate                                          PAA       Polyacrylic Acid (mw = 4500)                                        PEG       Polyethylene glycol (mw = 4600)                                     MES       Alkyl methyl ester sulfonate                                        SAS       Secondary alkyl sulfate                                             NaPS      Sodium paraffin sulfonate                                           STPP      Sodium Tri-polyphosphate                                            C45AS     Sodium C.sub.14 -C.sub.15 linear alkyl sulfate                      CxyEzS    Sodium C.sub.1x -C.sub.1y alkyl sulfate condensed                             with z moles of ethylene oxide                                      CxyEz     A C.sub.1x-1y branched primary alcohol condensed with an                      average of z moles of ethylene oxide                                QAS       R.sub.2.N.sup.+ (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with                    R.sub.2 = C.sub.12 -C.sub.14                                        TFAA      C.sub.16 -C.sub.18 alkyl N-methyl glucamide                         STPP      Anhydrous sodium tripolyphosphate                                   Zeolite A Hydrated Sodium Aluminosilicate of formula                                    Na.sub.12 (A10.sub.2 SiO.sub.2).sub.12. 27H.sub.2 O having a                  primary particle                                                              size in the range from 0.1 to 10 micrometers                        Na.sub.2 Si.sub.2 O.sub.5ered silicate of formula δ                     Carbonate Anhydrous sodium carbonate with a particle size                               between 200 μm and 900 μm                                     Bicarbonate                                                                             Anhydrous sodium bicarbonate with a particle size                             distribution between 400 μm and 1200 μm                       Silicate  Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O; 2.0 ratio)        Sodium sulfate                                                                          Anhydrous sodium sulfate                                            MA/AA     Copolymer of 1:4 maleic/acrylic acid, average                                 molecular weight about 70,000.                                      CMC       Sodium carboxymethyl cellulose                                      Protease  Proteolytic enzyme of activity 4KNPU/g sold by                                NOVO Industries A/S under the tradename Savinase                    Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by                             NOVO Industries A/S under the tradename                             Carezyme                                                                      Amylase   Amylolytic enzyme of activity 60KNU/g sold by                                 NOVO Industries A/S under the tradename Termamyl                              60T                                                                 Lipase    Lipolytic enzyme of activity 100kLU/g sold by NOVO                            Industries A/S under the tradename Lipolase                         PB4       Sodium perborate tetrahydrate of nominal formula                              NaBO.sub.2.3H.sub.2 O.H.sub.2 O.sub.2                               PB1       Anhydrous sodium perborate bleach of nominal                                  formula NaBO.sub.2.H.sub.2 O.sub.2                                  Percarbonate                                                                            Sodium Percarbonate of nominal formula                                        2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2                                 NaDCC     Sodium dichloroisocyanurate                                         NOBS      Nonanoyloxybenzene sulfonate in the form of the                               sodium salt.                                                        TAED      Tetraacetylethylenediamine                                          DTPMP     Diethylene triamine penta (methylene                                phosphonate),                                                                           marketed by Monsanto under the Trade name Dequest                             2060                                                                Photoactivated                                                                          Sulfonated Zinc Phthlocyanine encapsulated in bleach                          dextrin soluble polymer                                             Brightener 1                                                                            Disodium 4,4'-bis(2-sulphostyryl)biphenyl                           Brightener 2                                                                            Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-                     triazin-                                                                                2-yl)amino) stilbene-2:2'-disulfonate.                              HEDP      1,1-hydroxyethane diphosphonic acid                                 SRP 1     Sulfobenzoyl end capped esters with oxyethylene oxy                           and terephtaloyl backbone                                           Silicone antifoam                                                                       Polydimethylsiloxane foam controller with siloxane-                           oxyalkylene copolymer as dispersing agent with a ratio                        of said foam controller to said dispersing agent of 10:1                      to 100:1.                                                           DTPA      Diethylene triamine pentaacetic acid                                ______________________________________                                    

In the following Examples all levels are quoted as % by weight of thecomposition. The following examples are illustrative of the presentinvention, but are not meant to limit or otherwise define its scope. Allparts, percentages and ratios used herein are expressed as percentweight unless otherwise specified.

Example 1

The following laundry detergent compositions A to D are prepared inaccord with the invention:

    ______________________________________                                                   A     B         C       D                                          ______________________________________                                        MBAE0.5S (avg.                                                                             22      16.5      11    5.5                                      total carbons = 16.5)                                                         Any Combination of:                                                                        0       5.5       11    16.5                                     C45 AS                                                                        C45E1S                                                                        LAS                                                                           C16 SAS                                                                       C14-17 NaPS                                                                   C14-18 MES                                                                    C23E6.5      1.5     1.5       1.5   1.5                                      Zeolite A    27.8    27.8      27.8  27.8                                     PAA          2.3     2.3       2.3   2.3                                      Carbonate    27.3    27.3      27.3  27.3                                     Silicate     0.6     0.6       0.6   0.6                                      Perborate    1.0     1.0       1.0   1.0                                      Protease     0.3     0.3       0.3   0.3                                      Carezyme     0.3     0.3       0.3   0.3                                      SRP          0.4     0.4       0.4   0.4                                      Brightener   0.2     0.2       0.2   0.2                                      PEG          1.6     1.6       1.6   1.6                                      Sulfate      5.5     5.5       5.5   5.5                                      Silicone Antifoam                                                                          0.42    0.42      0.42  0.42                                     Moisture & Minors                                                                          Balance                                                          Density (g/L)                                                                              663     663       663   663                                      ______________________________________                                    

Example 2

The following laundry detergent compositions E to F are prepared inaccord with the invention:

    ______________________________________                                                   E     F       G       H     I                                      ______________________________________                                        MBAE0.5S (avg.                                                                             14.8    16.4    12.3  8.2   4.1                                  total carbons = 16.5)                                                         Any Combination of:                                                                        0       0       4.1   8.2   12.3                                 C45 AS                                                                        C45E1S                                                                        LAS                                                                           C16 SAS                                                                       C14-17 NaPS                                                                   C14-18 MES                                                                    TFAA         1.6     0       0     0     0                                    C24E3        4.9     4.9     4.9   4.9   4.9                                  Zeolite A    15      15      15    15    15                                   NaSKS-6      11      11      11    11    11                                   Citrate      3       3       3     3     3                                    MA/AA        4.8     4.8     4.8   4.8   4.8                                  HEDP         0.5     0.5     0.5   0.5   0.5                                  Carbonate    8.5     8.5     8.5   8.5   8.5                                  Percarbonate 20.7    20.7    20.7  20.7  20.7                                 TAED         4.8     4.8     4.8   4.8   4.8                                  Protease     0.9     0.9     0.9   0.9   0.9                                  Lipase       0.15    0.15    0.15  0.15  0.15                                 Carezyme     0.26    0.26    0.26  0.26  0.26                                 Amylase      0.36    0.36    0.36  0.36  0.36                                 SRP          0.2     0.2     0.2   0.2   0.2                                  Brightener   0.2     0.2     0.2   0.2   0.2                                  Sulfate      2.3     2.3     2.3   2.3   2.3                                  Silicone Antifoam                                                                          0.4     0.4     0.4   0.4   0.4                                  Moisture & Minors                                                                          Balance                                                          Density (g/L)                                                                              850     850           850   850                                  ______________________________________                                    

Example 3

The following laundry detergent compositions J to O are prepared inaccord with the invention:

    ______________________________________                                                  J     K      L       M    N     O                                   ______________________________________                                        MBAE0.5S (avg.                                                                            32      32     24    16   16    8                                 total carbons = 16.5)                                                         Any Combination of:                                                                       0       0      8     16   16    24                                C45 AS                                                                        C45E1S                                                                        LAS                                                                           C16 SAS                                                                       C14-17 NaPS                                                                   C14-18 MES                                                                    C23E6.5     3.6     3.6    3.6   3.6  3.6   3.6                               QAS         --      0.5    --    --   0.5   --                                Zeolite A   9.0     9.0    9.0   9.0  9.0   9.0                               Polycarboxylate                                                                           7.0     7.0    7.0   7.0  7.0   7.0                               Carbonate   18.4    18.4   18.4  18.4 18.4  18.4                              Silicate    11.3    11.3   11.3  11.3 11.3  11.3                              Perborate   3.9     3.9    3.9   3.9  3.9   3.9                               NOBS        4.1     4.1    4.1   4.1  4.1   4.1                               Protease    0.9     0.9    0.9   0.9  0.9   0.9                               SRP         0.5     0.5    0.5   0.5  0.5   0.5                               Brightener  0.3     0.3    0.3   0.3  0.3   0.3                               PEG         0.2     0.2    0.2   0.2  0.2   0.2                               Sulfate     5.1     5.1    5.1   5.1  5.1   5.1                               Silicone Antifoam                                                                         0.2     0.2    0.2   0.2  0.2   0.2                               Moisture & Minors                                                                         Balance                                                           Density (g/L)                                                                             810     810    810   810  810   810                               ______________________________________                                    

Example 4

The following laundry detergent compositions O to R are prepared inaccord with the invention:

    ______________________________________                                                     O    P         Q      R                                          ______________________________________                                        MBAE0.5S (avg. 22     16.5      11   5.5                                      total carbons = 16.5)                                                         Any Combination of:                                                                          0      5.5       11   16.5                                     C45 AS                                                                        C45E1S                                                                        LAS                                                                           C16 SAS                                                                       C14-17 NaPS                                                                   C14-18 MES                                                                    C23E6.5        1.2    1.2       1.2  1.2                                      STPP           35.0   35.0      35.0 35.0                                     Carbonate      19.0   19.0      19.0 19.0                                     Zeolite A      16.0   16.0      16.0 16.0                                     Silicate       2.0    2.0       2.0  2.0                                      CMC            0.3    0.3       0.3  0.3                                      Protease       1.4    1.4       1.4  1.4                                      Lipolase       0.12   0.12      0.12 0.12                                     SRP            0.3    0.3       0.3  0.3                                      Brightener     0.2    0.2       0.2  0.2                                      Moisture & Minors                                                                            Balance                                                        ______________________________________                                    

Example 5

The following liquid laundry detergent compositions AA to DD areprepared in accord with the invention:

    ______________________________________                                                   AA     BB       CC       DD                                        ______________________________________                                        MBAExS (x = 1.8-2.5;                                                                       6.5      11.5     16.5   21.5                                    14.5-15.5 ave. total                                                          carbon in alkyl group)                                                        Any combination of:                                                                        15       10       5      0                                       C25 AExS*Na                                                                   (x = 1.8-2.5)                                                                 C25 AS                                                                        (linear to high 2-alkyl)                                                      C14-17 NaPS                                                                   C12-16 SAS                                                                    C18 1,4 disulfate                                                             C11.3 LAS                                                                     C12-16 MES                                                                    LMFAA        2.5-3.5  2.5-3.5  2.5-3.5                                                                              2.5-3.5                                 C23E9        0.6-2    0.6-2    0.6-2  0.6-2                                   APA          0-0.5    0-0.5    0-0.5  0-0.5                                   Citric Acid  3.0      3.0      3.0    3.0                                     Fatty Acid   2.0      2.0      2.0    2.0                                     (TPK or C12/14)                                                               Ethanol      3.4      3.4      3.4    3.4                                     Propanediol  6.4      6.4      6.4    6.4                                     Monoethanol amine                                                                          1.0      1.0      1.0    1.0                                     NaOH         3.0      3.0      3.0    3.0                                     Na toluene sulfonate                                                                       2.3      2.3      2.3    2.3                                     Na formate   0.1      0.1      0.1    0.1                                     Borax        2-2.5    2-2.5    2-2.5  2-2.5                                   Protease     0.9      0.9      0.9    0.9                                     Lipase       0.04-0.08                                                                              0.04-0.08                                                                              0.04-0.08                                                                            0.04-0.08                               Amylase      0.15     0.15     0.15   0.15                                    Cellulase    0.05     0.05     0.05   0.05                                    Ethoxylated TEPA                                                                           1.2      1.2      1.2    1.2                                     SRP 2        0.1-0.2  0.1-0.2  0.1-0.2                                                                              0.1-0.2                                 Brightener 3 0.15     0.15     0.15   0.15                                    Silicone antifoam                                                                          0.12     0.12     0.12   0.12                                    Fumed Silica 0.0015   0.0015   0.0015 0.0015                                  Perfume      0.3      0.3      0.3    0.3                                     Dye          0.0013   0.00123  0.0013 0.0013                                  Moisture/minors                                                                            Balance  Balance  Balance                                                                              Balance                                 Product pH   7.7      7.7      7.7    7.7                                     (10% in DI water)                                                             ______________________________________                                    

Example 6

The following liquid laundry detergent compositions EE to II areprepared in accord with the invention:

    __________________________________________________________________________               EE    FF   GG    HH   II                                           __________________________________________________________________________    MBAExS (x = 1.8-2.5;                                                                     2     6.25 10.5  14.75                                                                              19                                           14.5-15.5 ave. total                                                          carbon in alkyl group)                                                        Any combination of:                                                                      17    12.75                                                                              8.5   4.25 0                                            C25 AExS*Na                                                                   (x = 1.8-2.5)                                                                 C25 AS                                                                        (linear to high 2-alkyl)                                                      C14-17 NaPS                                                                   C12-16 SAS                                                                    C18 1,4 disulfate                                                             C11.3 LAS                                                                     C12-16 MES                                                                    LMFAA      3.5-5.5                                                                             3.5-5.5                                                                            3.5-5.5                                                                             3.5-5.5                                                                            3.5-5.5                                      C23E9      4-6   4-6  4-6   4-6  4-6                                          APA        0-1.5 0-1.5                                                                              0-1.5 0-1.5                                                                              0-1.5                                        Citric Acid                                                                              1     1    1     1    1                                            Fatty Acid 7.5   7.5  7.5   7.5  7.5                                          (TPK or C12/14)                                                               Fatty Acid (Rapeseed)                                                                    3.1   3.1  3.1   3.1  3.1                                          Ethanol    1.8   1.8  1.8   1.8  1.8                                          Propanediol                                                                              9.4   9.4  9.4   9.4  9.4                                          Monoethanol amine                                                                        6.5   6.5  6.5   6.5  6.5                                          NaOH       1.5   1.5  1.5   1.5  1.5                                          Na toluene sulfonate                                                                     0-2   0-2  0-2   0-2  0-2                                          Borate (in ionic form)                                                                   2-2.5 2-2.5                                                                              2-2.5 2-2.5                                                                              2-2.5                                        CaCl2      0.02  0.02 0.02  0.02 0.02                                         Protease   0.48-0.6                                                                            0.48-0.6                                                                           0.48-0.6                                                                            0.48-0.6                                                                           0.48-0.6                                     Lipase     0.06-0.14                                                                           0.06-0.14                                                                          0.06-0.14                                                                           0.06-0.14                                                                          0.06-0.14                                    Amylase    0.06-0.14                                                                           0.06-0.14                                                                          0.06-0.14                                                                           0.06-0.14                                                                          0.06-0.14                                    Cellulase  0.03  0.03 0.03  0.03 0.03                                         Ethoxylated TEPA                                                                         0.2-0.7                                                                             0.2-0.7                                                                            0.2-0.7                                                                             0.2-0.7                                                                            0.2-0.7                                      SRP 3      0.1-0.2                                                                             0.1-0.2                                                                            0.1-0.2                                                                             0.1-0.2                                                                            0.1-0.2                                      Brightener 4                                                                             0.15  0.15 0.15  0.15 0.15                                         Silicone antifoam                                                                        0.2-0.25                                                                            0.2-0.25                                                                           0.2-0.25                                                                            0.2-0.25                                                                           0.2-0.25                                     Isofol 16  0-2   0-2  0-2   0-2  0-2                                          Fumed Silica                                                                             0.0015                                                                              0.0015                                                                             0.0015                                                                              0.0015                                                                             0.0015                                       Perfume    0.5   0.5  0.5   0.5  0.5                                          Dye        0.0013                                                                              0.0013                                                                             0.0013                                                                              0.0013                                                                             0.0013                                       Moisture/minors                                                                          Balance                                                                             Balance                                                                            Balance                                                                             Balance                                                                            Balance                                      Product pH 7.6   7.6  7.6   7.6  7.6                                          (10% in DI water)                                                             __________________________________________________________________________

Example 7

Branched ethoxylated surfactants are made by reaction of the appropriatebranched alcohols with ethylene oxide followed by sulfation as describedherein before. The branched alcohols are made from linear olefins (alphaand/or internal olefins) that have been molecularly re-arranged byexposure to appropriate catalysts. No additional carbons are added inthis re-arrangement, but the starting olefin is isomerized so that itnow contains one or more alkyl branches along the main alkyl chain. Asthe olefin moiety stays intact throughout this molecular re-arrangement,a --CH₂ OH group is then added via hydroformylation chemistry. Thefollowing Shell Research experimental test alcohol samples areethoxylated (average ethoxylation of 2) and then sulfated.

    ______________________________________                                        .sup.13 C-NMR Results For Branched Alcohols Prepared                          Total Number of Carbons                                                                        16        17     18                                          ______________________________________                                        Avg. Number of Branches per                                                                    2.0       1.7    2.1                                         Molecule                                                                      Average Branch Position Relative To                                           Hydroxyl Carbon                                                               % at C4 and higher                                                                             56%       55%    52%                                         % at C3          26%       21%    25%                                         % at C2          18%       24%    23%                                         Type of Branching                                                             % propyl and higher                                                                            31%       35%    30%                                         % ethyl          12%       10%    12%                                         % methyl         57%       55%    58%                                         ______________________________________                                    

Solutions of laundry prototype formulas are prepared as shown below.

    ______________________________________                                        PPM Ingredients In The Wash Solution                                                        A     B      C      D    E                                      ______________________________________                                        C11.9 alkyl benzene                                                                           92      --     --   --   --                                   sulfonate, sodium salt                                                        C14-15 sulfate, sodium salt                                                                   110     212    106  106  106                                  C14-15 ethoxy sulfate,                                                                        10      --     --   --   --                                   sodium salt                                                                   Neodol 23-6.5   15      15     15   15   15                                   C16 branched ethoxylate                                                                       50      --     106  --   --                                   (E2) sulfate, sodium salt                                                     C17 branched ethoxylate                                                                       50      50     --   106  --                                   (E2) sulfate, sodium salt                                                     C18 branched ethoxylate                                                                       --      50     --   --   106                                  (E2) sulfate, sodium salt                                                     Zeolite A       271     271    271  271  271                                  Sodium Carbonate                                                                              50      50     50   50   50                                   Sodium Sulfate  52      52     52   52   52                                   Sodium Perborate                                                                              10      10     10   10   10                                   Polyacrylic Acid (MW =                                                                        22      22     22   22   22                                   4500)                                                                         Polyethylene Glycol (MW =                                                                      9       9      9    9    9                                   4600)                                                                         Sodium Silicate  6       6      6    6    6                                   ______________________________________                                    

Example 8

Solutions of laundry prototype formulas are prepared as shown below.

    ______________________________________                                        PPM Ingredients In The Wash Solution                                                         F        G      H                                              ______________________________________                                        C11.9 alkyl benzene                                                                            144        144    144                                        sulfonate, sodium salt                                                        C14-15 sulfate, sodium salt                                                                    24         24     24                                         C14-15 ethoxy sulfate,                                                                          9          9      9                                         sodium salt                                                                   Neodol 23-6.5    15         15     15                                         C16 branched ethoxylate                                                                        73         --     --                                         (E2) sulfate, sodium salt                                                     C17 branched ethoxylate                                                                        --         73     --                                         (E2) sulfate, sodium salt                                                     C18 branched ethoxylate                                                                        --         --     73                                         (E2) sulfate, sodium salt                                                     Zeolite A        260        260    260                                        Sodium Carbonate 193        193    193                                        Sodium Sulfate   52         52     52                                         Sodium Perborate 10         10     10                                         Polyacrylic Acid (MW =                                                                         22         22     22                                         4500)                                                                         Polyethylene Glycol (MW =                                                                       9          9      9                                         4600)                                                                         Sodium Silicate   6          6      6                                         ______________________________________                                    

The manufacture of heavy duty liquid detergent compositions, especiallythose designed for fabric laundering, which comprise a non-aqueouscarrier medium can be conducted in the manner disclosed in more detailhereinafter. In an alternate mode, such non-aqueous compositions can beprepared according to the disclosures of U.S. Pat. Nos. 4,753,570;4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838;GB-A-2,195,125; GB-A-2,195,649; U.S. Pat. No. 4,988,462; U.S. Pat. No.5,266,233; EP-A-225,654 (Jun. 16,1987); EP-A-510,762 (Oct. 28,1992);EP-A-540,089 (May 5,1993); EP-A-540,090 (May 5,1993); U.S. Pat. No.4,615,820; EP-A-565,017 (Oct. 13,1993); EP-A-030,096 (Jun. 10,1981),incorporated herein by reference. Such compositions can contain variousparticulate detersive ingredients (including the bleaching agents, asdisclosed hereinabove) stably suspended therein. Such non-aqueouscompositions thus comprise a LIQUID PHASE and, optionally butpreferably, a SOLID PHASE, all as described in more detail hereinafterand in the cited references. The alkoxylated dianionic ester cleaningagent is incorporated in the compositions at the levels and in themanner described hereinabove for the manufacture of other laundrydetergent compositions.

Liquid Phase

The liquid phase will generally comprise from about 35% to 99% by weightof the detergent compositions herein. More preferably, the liquid phasewill comprise from about 50% to 95% by weight of the compositions. Mostpreferably, the liquid phase will comprise from about 45% to 75% byweight of the compositions herein. The liquid phase of the detergentcompositions herein essentially contains relatively high concentrationsof a certain type anionic surfactant combined with a certain type ofnonaqueous, liquid diluent.

(A) Essential Anionic Surfactant

The anionic surfactant essentially utilized as an essential component ofthe nonaqueous liquid phase is one selected from the alkali metal saltsof alkylbenzene sulfonic acids in which the alkyl group contains fromabout 10 to 16 carbon atoms, in straight chain or branched chainconfiguration. (See U.S. Pat. Nos. 2,220,099 and 2,477,383, incorporatedherein by reference.) Especially preferred are the sodium and potassiumlinear straight chain alkylbenzene sulfonates (LAS) in which the averagenumber of carbon atoms in the alkyl group is from about 11 to 14. SodumC₁₁ -C₁₄ LAS is especially preferred.

The alkylbenzene sulfonate anionic surfactant will be dissolved in thenonaqueous liquid diluent which makes up the second essential componentof the nonaqueous phase. To form the structured liquid phase requiredfor suitable phase stability and acceptable rheology, the alkylbenzenesulfonate anionic surfactant is generally present to the extent of fromabout 30% to 65% by weight of the liquid phase. More preferably, thealkylbenzene sulfonate anionic surfactant will comprise from about 35%to 50% by weight of the nonaqueous liquid phase of the compositionsherein. Utilization of this anionic surfactant in these concentrationscorresponds to an anionic surfactant concentration in the totalcomposition of from about 15% to 60% by weight, more preferably fromabout 20% to 40% by weight, of the composition.

(B) Nonaqueous Liquid Diluent

To form the liquid phase of the detergent compositions, the hereinbeforedescribed alkylbenzene sulfonate anionic surfactant is combined with anonaqueous liquid diluent which contains two essential components. Thesetwo components are a liquid alcohol alkoxylate material and anonaqueous, low-polarity organic solvent.

i) Alcohol Alkoxylates

One essential component of the liquid diluent used to form thecompositions herein comprises an alkoxylated fatty alcohol material.Such materials are themselves also nonionic surfactants. Such materialscorrespond to the general formula:

    R.sup.1 (OC.sub.m H.sub.2m).sub.n OH

wherein R¹ is a C₈ -C₁₆ alkyl group, m is from 2 to 4, and n ranges fromabout 2 to 12. Preferably R¹ is an alkyl group, which may be primary orsecondary, that contains from about 9 to 15 carbon atoms, morepreferably from about 10 to 14 carbon atoms. Preferably also thealkoxylated fatty alcohols will be ethoxylated materials that containfrom about 2 to 12 ethylene oxide moieties per molecule, more preferablyfrom about 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent willfrequently have a hydrophilic-lipophilic balance (HLB) which ranges fromabout 3 to 17. More preferably, the HLB of this material will range fromabout 6 to 15, most preferably from about 8 to 15.

Examples of fatty alcohol alkoxylates useful as one of the essentialcomponents of the nonaqueous liquid diluent in the compositions hereinwill include those which are made from alcohols of 12 to 15 carbon atomsand which contain about 7 moles of ethylene oxide. Such materials havebeen commercially marketed under the trade names Neodol 25-7 and Neodol23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkylchain with about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylatedprimary C₁₂ -C₁₃ alcohol having about 9 moles of ethylene oxide andNeodol 91-10, an ethoxylated C₉ -C₁₁ primary alcohol having about 10moles of ethylene oxide. Alcohol ethoxylates of this type have also beenmarketed by Shell Chemical Company under the Dobanol tradename. Dobanol91-5 is an ethoxylated C₉ -C₁₁ fatty alcohol with an average of 5 molesethylene oxide and Dobanol 25-7 is an ethoxylated C₁₂ -C₁₅ fatty alcoholwith an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7and Tergitol 15-S-9 both of which are linear secondary alcoholethoxylates that have been commercially marketed by Union CarbideCorporation. The former is a mixed ethoxylation product of C₁₁ to C₁₅linear secondary alkanol with 7 moles of ethylene oxide and the latteris a similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol ethoxylates useful in the present compositionsare higher molecular weight nonionics, such as Neodol 45-11, which aresimilar ethylene oxide condensation products of higher fatty alcohols,with the higher fatty alcohol being of 14-15 carbon atoms and the numberof ethylene oxide groups per mole being about 11. Such products havealso been commercially marketed by Shell Chemical Company.

The alcohol alkoxylate component which is essentially utilized as partof tle liquid diluent in the nonaqueous compositions herein willgenerally be present to the extent of from about 1% to 60% of the liquidphase composition. More preferably, the alcohol alkoxylate componentwill comprise about 5% to 40% of the liquid phase. Most preferably, theessentially utilized alcohol alkoxylate component will comprise fromabout 5% to 30% of the detergent composition liquid phase. Utilizationof alcohol alkoxylate in these concentrations in the liquid phasecorresponds to an alcohol alkoxylate concentration in the totalcomposition of from about 1% to 60% by weight, more preferably fromabout 2% to 40% by weight, and most preferably from about 5% to 25% byweight, of the composition.

ii) Nonaqueous Low-Polarity Organic Solvent

A second essential component of the liquid diluent which forms part ofthe liquid phase of the detergent compositions herein comprisesnonaqueous, low-polarity organic solvent(s). The term "solvent" is usedherein to connote the non-surface active carrier or diluent portion ofthe liquid phase of the composition. While some of the essential and/oroptional components of the compositions herein may actually dissolve inthe "solvent"-containing liquid phase, other components will be presentas particulate material dispersed within the "solvent"-containing liquidphase. Thus the term "solvent" is not meant to require that the solventmaterial be capable of actually dissolving all of the detergentcomposition components added thereto.

The nonaqueous organic materials which are employed as solvents hereinare those which are liquids of low polarity. For purposes of thisinvention, "low-polarity" liquids are those which have little, if any,tendency to dissolve one of the preferred types of particulate materialused in the compositions herein, i.e., the peroxygen bleaching agents,sodium perborate or sodium percarbonate. Thus relatively polar solventssuch as ethanol should not be utilized. Suitable types of low-polaritysolvents useful in the nonaqueous liquid detergent compositions hereindo include non-vicinal C₄ -C₈ alkylene glycols, alkylene glycol monolower alkyl ethers, lower molecular weight polyethylene glycols, lowermolecular weight methyl esters and amides, and the like.

A preferred type of nonaqueous, low-polarity solvent for use in thecompositions herein comprises the non-vicinal C₄ -C₈ branched orstraight chain alkylene glycols. Materials of this type include hexyleneglycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycoland 1,4-butylene glycol. Hexylene glycol is the most preferred.

Another preferred type of nonaqueous, low-polarity solvent for useherein comprises the mono-, di-, tri-, or tetra- C₂ -C₃ alkylene glycolmono C₂ -C₆ alkyl ethers. The specific examples of such compoundsinclude diethylene glycol monobutyl ether, tetraethylene glycolmonobutyl ether, dipropylene glycol monoethyl ether, and dipropyleneglycol monobutyl ether. Diethylene glycol monobutyl ether anddipropylene glycol monobutyl ether are especially preferred. Compoundsof the type have been commercially marketed under the tradenamesDowanol, Carbitol, and Cellosolve.

Another preferred type of nonaqueous, low-polarity organic solventuseful herein comprises the lower molecular weight polyethylene glycols(PEGs). Such materials are those having molecular weights of at leastabout 150. PEGs of molecular weight ranging from about 200 to 600 aremost preferred.

Yet another preferred type of non-polar, nonaqueous solvent compriseslower molecular weight methyl esters. Such materials are those of thegeneral formula: R¹ --C(O)--OCH₃ wherein R¹ ranges from 1 to about 18.Examples of suitable lower molecular weight methyl esters include methylacetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The nonaqueous, low-polarity organic solvent(s) employed should, ofcourse, be compatible and non-reactive with other compositioncomponents, e.g., bleach and/or activators, used in the liquid detergentcompositions herein. Such a solvent component will generally be utilizedin an amount of from about 1% to 70% by weight of the liquid phase. Morepreferably, the nonaqueous, low-polarity organic solvent will comprisefrom about 10% to 60% by weight of the liquid phase, most preferablyfrom about 20% to 50% by weight, of the liquid phase of the composition.Utilization of this organic solvent in these concentrations in theliquid phase corresponds to a solvent concentration in the totalcomposition of from about 1% to 50% by weight, more preferably fromabout 5% to 40% by weight, and most preferably from about 10% to 30% byweight, of the composition.

iii) Alcohol Alkoxylate To Solvent Ratio

The ratio of alcohol alkoxylate to organic solvent within the liquiddiluent can be used to vary the rheological properties of the detergentcompositions eventually formed. Generally, the weight ratio of alcoholalkoxylate to organic solvent will range from about 50:1 to 1:50. Morepreferably, this ratio will range from about 3:1 to 1:3.

iv) Liquid Diluent Concentration

As with the concentration of the alkylbenzene sulfonate anionicsurfactant mixture, the amount of total liquid diluent in the nonaqueousliquid phase herein will be determined by the type and amounts of othercomposition components and by the desired composition properties.Generally, the liquid diluent will comprise from about 35% to 70% of thenonaqueous liquid phase of the compositions herein. More preferably, theliquid diluent will comprise from about 50% to 65% of the nonaqueousliquid phase. This corresponds to a nonaqueous liquid diluentconcentration in the total composition of from about 15% to 70% byweight, more preferably from about 20% to 50% by weight, of thecomposition.

Solid Phase

The nonaqueous detergent compositions herein also essentially comprisefrom about 1% to 65% by weight, more preferably from about 5% to 50% byweight, of a solid phase of particulate material which is dispersed andsuspended within the liquid phase. Generally such particulate materialwill range in size from about 0.1 to 1500 microns. More preferably suchmaterial will range in size from about 5 to 200 microns.

The particulate material utilized herein can comprise one or more typesof detergent composition components which in particulate form aresubstantially insoluble in the nonaqueous liquid phase of thecomposition. The types of particulate materials which can be utilizedare described in detail as follows:

Composition Preparation and Use

The nonaqueous liquid detergent compositions herein can be prepared bycombining the essential and optional components thereof in anyconvenient order and by mixing, e.g., agitating, the resulting componentcombination to form the phase stable compositions herein. In a typicalprocess for preparing such compositions, essential and certain preferredoptional components will be combined in a particular order and undercertain conditions.

In the first step of such a typical preparation process, an admixture ofthe alkylbenzene sulfonate anionic surfactant and the two essentialcomponents of the nonaqueous diluent is formed by heating a combinationof these materials to a temperature from about 30° C. to 100° C.

In a second process step, the heated admixture formed as hereinbeforedescribed is maintained under shear agitation at a temperature fromabout 40° C. to 100° C. for a period of from about 2 minutes to 20hours. Optionally, a vacuum can be applied to the admixture at thispoint. This second process step serves to completely dissolve theanionic surfactant in the nonaqueous liquid phase.

In a third process step, this liquid phase combination of materials iscooled to a temperature of from about 0° C. to 35° C. This cooling stepserves to form a structured, surfactant-containing liquid base intowhich the particulate material of the detergent compositions herein canbe added and dispersed.

Particulate material is added in a fourth process step by combining theparticulate material with the liquid base which is maintained underconditions of shear agitation. When more than one type of particulatematerial is to be added, it is preferred that a certain order ofaddition be observed. For example, while shear agitation is maintained,essentially all of any optional surfactants in solid particulate formcan be added in the form of particles ranging in size from about 0.2 to1,000 microns. After addition of any optional surfactant particles,particles of substantially all of an organic builder, e.g., citrateand/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate,can be added while continuing to maintain this admixture of compositioncomponents under shear agitation. Other solid form optional ingredientscan then be added to the composition at this point. Agitation of themixture is continued, and if necessary, can be increased at this pointto form a uniform dispersion of insoluble solid phase particulateswithin the liquid phase.

After some or all of the foregoing solid materials have been added tothis agitated mixture, the particles of the bleaching agent can be addedto the composition, again while the mixture is maintained under shearagitation. By adding the bleaching agent material last, or after all ormost of the other components, and especially after alkalinity sourceparticles, have been added, desirable stability benefits for the bleachcan be realized. If enzyme prills are incorporated, they are preferablyadded to the nonaqueous liquid matrix last.

As a final process step, after addition of all of the particulatematerial, agitation of the mixture is continued for a period of timesufficient to form compositions having the requisite viscosity and phasestability characteristics. Frequently this will involve agitation for aperiod of from about 1 to 30 minutes.

As a variation of the composition preparation procedure hereinbeforedescribed, one or more of the solid components may be added to theagitated mixture as a slurry of particles premixed with a minor portionof one or more of the liquid components. Thus a premix of a smallfraction of the alcohol alkoxylate and/or nonaqueous, low-polaritysolvent with particles of the organic builder material and/or theparticles of the inorganic alkalinity source and/or particles of ableach activator may be separately formed and added as a slurry to theagitated mixture of composition components. Addition of such slurrypremixes should precede addition of bleaching agent and/or enzymeparticles which may themselves be part of a premix slurry formed inanalogous fashion.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingand bleaching of fabrics. Generally, an effective amount of suchcompositions is added to water, preferably in a conventional fabriclaundering automatic washing machine, to form such aqueouslaundering/bleaching solutions. The aqueous washing/bleaching solutionso formed is then contacted, preferably under agitation, with thefabrics to be laundered and bleached therewith.

An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering/bleaching solutions can compriseamounts sufficient to form from about 500 to 7,000 ppm of composition inaqueous solution. More preferably, from about 800 to 3,000 ppm of thedetergent compositions herein will be provided in aqueouswashing/bleaching solution.

Example 9

A non-limiting example of bleach-containing nonaqueous liquid laundrydetergent is prepared having the composition as set forth in Table I.

                  TABLE I                                                         ______________________________________                                        Component            Wt. %    Range (% wt.)                                   ______________________________________                                        Liquid Phase                                                                  Na C.sub.12 Linear alkylbenzene sulfonate (LAS)                                                    25.3     18-35                                           MBAE.sub.2 S.sub.16.5                                                                              2.0       1-10                                           C.sub.12-14, EO5 alcohol ethoxylate                                                                13.6     10-20                                           Hexylene glycol      27.3     20-30                                           Perfume              0.4        0-1.0                                         Solids                                                                        Protease enzyme      0.4        0-1.0                                         Na.sub.3 Citrate, anhydrous                                                                        4.3      3-6                                             Sodium perborate     3.4      2-7                                             Sodium nonanoyloxybenzene sulfonate                                                                8.0       2-12                                           (NOBS)                                                                        Sodium carbonate     13.9      5-20                                           Diethyl triamine pentaacetic acid (DTPA)                                                           0.9        0-1.5                                         Brightener           0.4        0-0.6                                         Suds Suppressor      0.1        0-0.3                                         Minors               Balance  --                                              ______________________________________                                    

The resulting composition is a stable anhydrous heavy duty liquidlaundry detergent which provides excellent stain and soil removalperformance when used in normal fabric laundering operations.

The following Example further illustrates the invention herein withrespect to a hand dishwashing liquid.

Example

    ______________________________________                                        Ingredient         % (wt.)  Range (% wt.)                                     ______________________________________                                        MBAE.sub.2 S.sub.16.5                                                                            2.0      0.15-15                                           Ammonium C.sub.12-13 alkyl sulfate                                                               7.0      2-35                                              C.sub.12 -C.sub.14 ethoxy (1) sulfate                                                            20.5     5-35                                              Coconut amine oxide                                                                              2.6      2-5                                               Betaine/Tetronic 704 ®**                                                                     0.87-0.10                                                                              0-2 (mix)                                         Alcohol Ethoxylate C.sub.9-11 E.sub.9                                                            5.0      2-10                                              Ammonium xylene sulfonate                                                                        4.0      1-6                                               Ethanol            4.0      0-7                                               Ammonium citrate   0.06     0-1.0                                             Magnesium chloride 3.3      0-4.0                                             Calcium chloride   2.5      0-4.0                                             Ammonium sulfate   0.08     0-4.0                                             Hydrogen peroxide  200 ppm  10-300 ppm                                        Perfume            0.18     0-0.5                                             Maxatase ® protease                                                                          0.50     0-1.0                                             Water and minors                                                              Balance-----------                                                            ______________________________________                                         **Cocoalkyl betaine.                                                     

The following Examples further illustrate the invention herein withrespect to a granular phosphate-containing automatic dishwashingdetergent.

Example

    ______________________________________                                                      % by weight of active material                                  INGREDIENTS     A          B                                                  ______________________________________                                        STPP (anhydrous).sup.1                                                                        31         26                                                 MBAE.sub.2 S.sub.16.5                                                                          1         1                                                  Sodium Carbonate                                                                              22         32                                                 Silicate (% S.sub.i O.sub.2)                                                                   9         7                                                  Surfactant (nonionic)                                                                          3         1.5                                                NaDCC Bleach.sup.2                                                                             2         --                                                 Sodium Perborate                                                                              --         5                                                  TAED            --         1.5                                                Savinase (Au/g) --         0.04                                               Termamyl (Amu/g)           425                                                Sulfate         25         25                                                 Perfume/Minors  to 100%    to 100%                                            ______________________________________                                         .sup.1 Sodium tripoly phosphate                                               .sup.2 Sodium dichloro cyanurate                                         

What is claimed is:
 1. A surfactant composition comprising comprising from about 0.001% to about 100% of one or more mid-chain branched primary alkyl alkoxylated sulfates having the formula: ##STR36## wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, R¹, and R³ branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃ alkyl, preferably methyl, provided R, R¹, and R² are not all hydrogen and, when z is 1, at least R or R¹ is not hydrogen; M is one or more cations; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; w+x+y+z is from 8 to 14; and EO/PO are alkoxy moieties, selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01.
 2. A composition according to claim 1 wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups.
 3. A composition according to claim 1 wherein R, R¹, and R² are each independently selected from hydrogen and methyl.
 4. A composition according to claim 1 wherein M is selected from the group consisting of sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula ##STR37## wherein R³, R⁴, R⁵ and R⁶ are independently selected from hydrogen, C₁ -C₂₂ alkylene, C₄ -C₂₂ branched alkylene, C₁ -C₆ alkanol, C₁ -C₂₂ alkenylene, C₄ -C₂₂ branched alkenylene, and mixtures thereof.
 5. A composition according to claim 1 wherein M is sodium, potassium, and mixtures thereof.
 6. A composition according to claim 1 wherein at least 5% of the mixture comprises one or more mid-chain branched primary alkyl alkoxylated sulfates wherein z is at least
 2. 7. A composition according to claim 1 wherein at least 20% of the mixture comprises one or more mid-chain branched primary alkyl alkoxylated sulfates wherein z is at least
 2. 8. A composition according to claim 1 wherein at least 5% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 0.1 to about
 30. 9. A composition according to claim 1 wherein at least 20% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 0.5 to about
 10. 10. A composition according to claim 1 wherein at least 5% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 1 to about
 5. 11. A composition according to claim 1 wherein at least 20% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 1 to about
 5. 12. A composition according to claim 1 wherein at least 0.001%, of the mixture comprises one or more mid-chain branched primary alkyl alkoxylated sulfates having the formula ##STR38## wherein R¹ and R² are each independently hydrogen or C₁ -C₃ alkyl; M is a water soluble cation; x is from 0 to 12; y is from 0 to 12; z is at least 2; x+y+z is from 11 to 14; and EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, provided R¹ and R² are not both hydrogen.
 13. A surfactant composition comprising a mixture of branched primary alkyl alkoxylated sulfates having the formula ##STR39## wherein the total number of carbon atoms per molecule, including branching, is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; R, R¹, and R² are each independently selected from hydrogen and C₁ -C₃ alkyl, provided R, R¹, and R² are not all hydrogen; M is a water soluble cation; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; w+x+y+z is from 8 to 14; EO/PO are alkoxy moieties, selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, provided that when R² is C₁ -C₃ alkyl the ratio of surfactants having z equal to 2 or greater to surfactants having z of 1 is at least about 1:1.
 14. A composition according to claim 13 wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups.
 15. A composition according to claim 13 comprising less than about 50%, of branched primary alkyl alkoxylated sulfate having the above formula wherein z equals 1 when R² is C₁ -C₃ alkyl.
 16. A detergent composition comprising(a) from about 0.001% to about 99% of one or more mid-chain branched primary alkyl alkoxylated sulfate surfactants having the formula: ##STR40## or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d+e=12, d is an integer from 2to 11 and e is an integer from 1 to 10; when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5; andwherein EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01; and (b) from about 1% to about 99.999% by weight of one or more detergent adjunct ingredients.
 17. A composition according to claim 16 wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups.
 18. A composition according to claim 16 wherein M is selected from the group consisting of sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula ##STR41## wherein R³, R⁴, R⁵ and R⁶ are independently selected from hydrogen, C₁ -C₂₂ alkylene, C₄ -C₂₂ branched alkylene, C₁ -C₆ alkanol, C₁ -C₂₂ alkenylene, C₄ -C₂₂ branched alkenylene, and mixtures thereof.
 19. A composition according to claim 16 wherein M is sodium, potassium, and mixtures thereof.
 20. A composition according to claim 16 wherein at least 5% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 0.1 to about
 30. 21. A composition according to claim 16 wherein at least 20% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 0.5 to about
 10. 22. A composition according to claim 16 wherein at least 5% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 1 to about
 5. 23. A composition according to claim 16 wherein at least 20% of the mixture comprises mid-chain branched primary alkyl alkoxylated sulfates wherein m is within the range of from about 1 to about
 5. 24. A mid-chain branched primary alkyl alkoxylated sulfate surfactants having the formula ##STR42## wherein R¹ and R² are each independently hydrogen or C₁ -C₃ alkyl; M is a water soluble cation; x is from 0 to 12; y is from 0 to 12; z is at least 2; x+y+z is from 11 to 14; and EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, provided R¹ and R² are not both hydrogen.
 25. A compound according to claim 24 wherein M is selected from the group consisting of sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula ##STR43## wherein R³, R⁴, R⁵ and R⁶ are independently selected from hydrogen, C₁ -C₂₂ alkylene, C₄ -C₂₂ branched alkylene, C₁ -C₆ alkanol, C₁ -C₂₂ alkenylene, C₄ -C₂₂ branched alkenylene, and mixtures thereof.
 26. A compound according to claim 25 wherein M is sodium, potassium, and mixtures thereof.
 27. A mid-chain branched alkyl alkoxylated sulfate compound of formula: ##STR44## wherein: a is an integer from 2 to 11, b is an integer from 1 to 10, and a+b is 12 or 13; and M is selected from sodium, potassium, magnesium, ammonium and substituted ammonium, and EO/PO are alkoxy moieties, selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about
 5. 28. A mid-chain branched alkyl alkoxylated sulfate compound of the formula: ##STR45## wherein: d and e are integers and d+e is 10 or 11; and wherein furtherwhen d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to 9; and M is selected from sodium, potassium, ammonium and substituted ammonium; and EO/PO are alkoxy moieties, selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01.
 29. Mono-methyl branched primary alkyl ethoxylated sulfates selected from the group consisting of: 3-methyl pentadecanol ethoxylated sulfate, 4-methyl pentadecanol ethoxylated sulfate, 5-methyl pentadecanol ethoxylated sulfate, 6-methyl pentadecanol ethoxylated sulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-methyl pentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylated sulfate, 10-methyl pentadecanol ethoxylated sulfate, 11-methyl pentadecanol ethoxylated sulfate, 12-methyl pentadecanol ethoxylated sulfate, 13-methyl pentadecanol ethoxylated sulfate, 3-methyl hexadecanol ethoxylated sulfate, 4-methyl hexadecanol ethoxylated sulfate, 5-methyl hexadecanol ethoxylated sulfate, 6-methyl hexadecanol ethoxylated sulfate, 7-methyl hexadecanol ethoxylated sulfate, 8-methyl hexadecanol ethoxylated sulfate, 9-methyl hexadecanol ethoxylated sulfate, 10-methyl hexadecanol ethoxylated sulfate, 11-methyl hexadecanol ethoxylated sulfate, 12-methyl hexadecanol ethoxylated sulfate, 13-methyl hexadecanol ethoxylated sulfate, 14-methyl hexadecanol ethoxylated sulfate, and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about
 10. 30. Di-methyl branched primary alkyl ethoxylated sulfates selected from the group consisting of: 2,3-methyl tetradecanol ethoxylated sulfate, 2,4-methyl tetradecanol ethoxylated sulfate, 2,5-methyl tetradecanol ethoxylated sulfate, 2,6-methyl tetradecanol ethoxylated sulfate, 2,7-methyl tetradecanol ethoxylated sulfate, 2,8-methyl tetradecanol ethoxylated sulfate, 2,9-methyl tetradecanol ethoxylated sulfate, 2,10-methyl tetradecanol ethoxylated sulfate, 2,11-methyl tetradecanol ethoxylated sulfate, 2,12-methyl tetradecanol ethoxylated sulfate, 2,3-methyl pentadecanol ethoxylated sulfate, 2,4-methyl pentadecanol ethoxylated sulfate, 2,5-methyl pentadecanol ethoxylated sulfate, 2,6-methyl pentadecanol ethoxylated sulfate, 2,7-methyl pentadecanol ethoxylated sulfate, 2,8-methyl pentadecanol ethoxylated sulfate, 2,9-methyl pentadecanol ethoxylated sulfate, 2,10-methyl pentadecanol ethoxylated sulfate, 2,11-methyl pentadecanol ethoxylated sulfate, 2,12-methyl pentadecanol ethoxylated sulfate, 2,13-methyl pentadecanol ethoxylated sulfate, and mixtures thereof, wherein the compounds are ethoxylated with an average degree of ethoxylation of from about 0.1 to about
 10. 